WO2019208710A1 - Procédé de production d'alcool alicyclique et d'aldéhyde - Google Patents

Procédé de production d'alcool alicyclique et d'aldéhyde Download PDF

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WO2019208710A1
WO2019208710A1 PCT/JP2019/017681 JP2019017681W WO2019208710A1 WO 2019208710 A1 WO2019208710 A1 WO 2019208710A1 JP 2019017681 W JP2019017681 W JP 2019017681W WO 2019208710 A1 WO2019208710 A1 WO 2019208710A1
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compound
reaction
catalyst
dodecane
pressure
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Japanese (ja)
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純 金田
悠祐 大形
弘樹 ▲高▼橋
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Ｋｈネオケム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/137—Monohydroxylic alcohols containing saturated rings polycyclic with condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/28—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
    • C07C47/34—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings polycyclic
    • C07C47/347—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings polycyclic having a —CHO group on a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .. which is a raw material for polymers used for optical materials, electrical / electronic materials and the like. 1, 7, 10 ] relates to a method for producing dodecane and the like.
  • Polymers such as poly (meth) acrylic acid ester, epoxy resin, polycarbonate, polyester, cycloolefin polymer, cycloolefin copolymer, vinyl alicyclic hydrocarbon polymer have excellent transparency, heat resistance, low hygroscopicity, etc. It has physical properties and is used for optical materials such as lenses and films.
  • 3-hydroxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane is known to be used as a raw material for the above polymer, and the conventional 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .
  • Patent Document 1 discloses 2-hydroxymethylbicyclo [2.2.1] -5-heptene and cyclohexane obtained by subjecting 2-formylbicyclo [2.2.1] -5-heptene to a hydrogenation reaction.
  • a Diels-Alder reaction with pentadiene was carried out to give 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .
  • Patent Document 2 discloses that a Diels-Alder reaction between dicyclopentadiene and allyl acetate is performed, and the resulting product is subjected to a hydrogenation reaction and then subjected to a hydrolysis reaction to give 3-hydroxymethyltetracyclohexane.
  • a method for producing dodecane is disclosed.
  • 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .
  • None of the production methods of [ 1,7,10 ] dodecane are sufficient.
  • the above-mentioned patent document discloses 3-hydroxymethyltetracyclo [4.4.0.1 2,5 . [ 1,7,10 ] No specific stereoisomer of dodecane is described.
  • Patent Document 3 methoxycarbonyltetracyclo [4.4.0.1 2,5 .
  • a process for producing a bifunctional compound having a norbornane skeleton by subjecting 1 7,10 ] -3-dodecene to a hydroformylation reaction followed by a hydrogenation reaction is described.
  • the object of the present invention is to provide 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .., which is a raw material for polymers used in optical materials, electrical / electronic materials, and the like. It is an object of the present invention to provide a method for producing 1 7,10 ] dodecane and the like in a high yield and with a high selectivity to a specific stereoisomer.
  • the present invention provides the following [1] to [5].
  • [1] Tetracyclo [4.4.0.1 2,5 . 1-7,10 ] -3-dodecene is subjected to a hydroformylation reaction followed by a hydrogenation reaction, characterized in that 3-hydroxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ]
  • a method for producing dodecane [2] 3-hydroxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane is the formula (1)
  • a compound represented by tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene is represented by the formula (2) [1]
  • 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .. which is a raw material for a polymer used in optical materials, electrical / electronic materials, and the like. It is possible to provide a method for producing [ 1,7,10 ] dodecane in a high yield and with a high selectivity to a specific stereoisomer.
  • 1 is a 1 H-NMR spectrum of a compound obtained in Example 2.
  • 2 is a NOESY-NMR spectrum of the compound obtained in Example 2.
  • 3-hydroxymethyltetracyclo produced by the production method of the present invention [4.4.0.1 2,5 . 1 7, 10 ] dodecane (hereinafter referred to as hydroxymethyl form) may have any stereostructure or a mixture thereof, but compound (1) having a single stereostructure, or compound (1 ) And a hydroxymethyl compound having a steric structure other than compound (1) (hereinafter referred to as an isomer of compound (1)) is preferred, and compound (1) is more preferred.
  • 3-formyltetracyclo produced by the production method of the present invention [4.4.0.1 2,5 .
  • dodecane (hereinafter referred to as formyl form) may be any steric structure or a mixture thereof, but compound (3) or compound (3) having a single steric structure And a mixture containing a formyl body having a steric structure other than the compound (3) (hereinafter referred to as an isomer of the compound (3)) is preferred, and a compound (3) is more preferred.
  • the hydroxymethyl compound is tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (hereinafter referred to as raw material olefin) is subjected to a hydroformylation reaction to obtain a hydroformylation reaction product, and then the resulting hydroformylation reaction product is subjected to a hydrogenation reaction. can do.
  • the hydroformylation reaction is carried out in the presence of a catalyst and a mixed gas of carbon monoxide and hydrogen.
  • the hydroformylation reaction product can be obtained as a formyl compound or a mixture of a formyl compound and a hydroxymethyl compound.
  • the formyl body can be produced by subjecting the raw olefin to a hydroformylation reaction.
  • the raw material olefin in this invention may use a commercially available thing, and may manufacture it according to a well-known method.
  • S.I. B. Soloway, J.A. Am. Chem. Soc. , 1952, 74 (4), pp 1027-1029, by subjecting norbornene and cyclopentadiene to Diels-Alder reaction.
  • a catalyst used in a general hydroformylation reaction for example, a known metal catalyst such as a cobalt-based catalyst, a rhodium-based catalyst, or a platinum-based catalyst can be used. Of these, a cobalt-based catalyst or a rhodium-based catalyst is preferable from the viewpoint of reaction rate and yield.
  • a metal catalyst a metal carbonyl complex compound, an arbitrary compound capable of forming a metal carbonyl complex compound in the reaction system, and the like can be used, and a metal catalyst supported on an appropriate carrier such as silica gel or activated carbon can also be used.
  • metal catalysts include the metal oxides, acetylacetonate salts, various carboxylates, sodium salts, chlorides, carbonyl complexes, triphenylphosphine complexes, and the like.
  • 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.
  • C 5 H 5 represents a cyclopentadienyl group
  • cobalt oxide cobalt acetate, cobalt 2-ethylhexanoate, Rh 4 (CO) 12 , Rh 6 (CO) 16 , rhodium acetate, 2 - ethylhexanoate rhodium, (..
  • acac is the same or less representative of the acetyl acetonate group) rhodium stearate, Rh (acac) 3, Rh (acac) (CO) 2, Rh (acac) (c d) (wherein, cod represents 1,4-cyclooctadienyl group.), RhCl 3, RhCl ( PPh 3) 3, ( wherein, Ph is the same. below represents a phenyl group.), RhH (CO) (PPh 3 ) 3 and the like.
  • These metal catalysts may be used alone or in combination of two or more.
  • the catalyst concentration in the case of using a rhodium-based catalyst is usually 0.1 to 1000 ppm, preferably 0.5 to 500 ppm, more preferably, as the weight concentration of rhodium atoms in the reaction mixture, from the viewpoint of reaction rate, economy and the like. Is in the 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, more preferably 100 to 3000 ppm as the weight concentration of cobalt atoms in the reaction mixture from the viewpoint of reaction rate, economy and the like. It is in the range. Further, an excessive amount of an organophosphorus compound may coexist with these catalysts.
  • the organic phosphorus compound is not particularly limited, phosphine or the general formula represented by the general formula R 1 3 P (R 2 O ) phosphite represented by 3 P and the like.
  • 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, or the like.
  • an alkyl group having 1 to 12 carbon atoms a phenyl group optionally substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a sulfone group;
  • an alicyclic alkyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms examples include a cyclohexyl group.
  • Bicyclic heterocyclic phosphines can also be used.
  • triphenylphosphine tritolylphosphine, tris (2-methylphenyl) phosphine, sodium triphenylphosphine trisulfonate, tricyclohexylphosphine, tri-n-butylphosphine, 9-phosphabicyclo [3.
  • organic phosphorus compounds may be used independently and may use 2 or more types together.
  • the amount of these organophosphorus compounds used is usually from 1 to 2000 times, preferably from 3 to 1000 times, more preferably from 1 to 2000 times the metal (rhodium, cobalt, etc.) in terms of catalyst life and reaction selectivity. It is in the range of 5 to 500 mole times.
  • the hydroformylation reaction can be carried out without using a solvent, but a solvent can also be used.
  • the solvent is not particularly limited as long as it dissolves the raw material olefin, the metal catalyst, and the organophosphorus compound.
  • Specific examples include alcohols such as ethanol, isopropyl alcohol, butanol, 2-ethylhexanol, 2-octanol, butyl acetate, cyclohexyl acetate, dibutyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate, phthalic acid Esters such as diisodecyl and triisononyl trimellitic acid, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, decane, dodecane, and tetradecane, cyclohexane, methylcyclohe
  • the temperature of the hydroformylation reaction is usually in the range of 40 to 180 ° C., preferably 60 to 170 ° C., more preferably 80 to 160 ° C. It is more preferable to carry out the reaction at a temperature of 40 ° C. or higher because the reaction rate is improved. Moreover, it is more preferable to carry out the reaction at a temperature of 180 ° C. or lower because the amount of by-products is reduced and the yield of the reaction is improved.
  • the hydroformylation reaction is preferably carried out under pressure with a mixed gas of carbon monoxide and hydrogen (hereinafter referred to as synthesis gas).
  • carbon monoxide and hydrogen can be independently introduced into the reaction system, or synthesis gas can be prepared in advance and introduced into the reaction system.
  • a gas inert to the hydroformylation reaction such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide, or the like may coexist.
  • the hydroformylation reaction is preferably carried out at a pressure usually in the range of 0.2 to 40 MPaG.
  • the pressure in the case of using a catalyst precursor without using an organic phosphorus compound is usually in the range of 10 to 30 MPaG, preferably 15 to 28 MPaG, more preferably 18 to 26 MPaG.
  • the pressure is usually in the range of 10 to 30 MPaG, preferably 15 to 28 MPaG, more preferably 18 to 26 MPaG.
  • the pressure is usually in the range of 0.3 to 30 MPaG, preferably 0.5 to 20 MPaG, more preferably 0.7 to 10 MPaG.
  • the pressure is usually in the range of 0.3 to 30 MPaG, preferably 0.5 to 20 MPaG, more preferably 0.7 to 10 MPaG.
  • the reaction form of the hydroformylation reaction is not particularly limited, and it can be carried out either batchwise using a known reaction apparatus or continuous. Specifically, it can be carried out in any of a stirring reaction tank, a tower reaction tank, and a tubular reaction tank.
  • the hydroformylation reaction product obtained after completion of the hydroformylation reaction may be used as it is as a raw material for the hydrogenation reaction in the next step, purified by a known method, and formyl, hydroxymethyl, and a part of the catalyst or All may be used as raw materials for the hydrogenation reaction in the next step after separation or removal.
  • a purification method in the case of purifying by a known method, for example, methods such as adsorption, extraction, neutralized water washing, distillation, crystallization and the like can be used, and these methods can be used in appropriate combination.
  • a cobalt-based catalyst it is preferable to go through a neutralization washing step. For example, after completion of the hydroformylation reaction, the cobalt-based catalyst is extracted and removed by adding an aqueous solution of an alkali metal compound or an alkaline earth metal compound to the system. can do.
  • the alkali metal compound or alkaline earth metal compound include hydroxides such as lithium, sodium, potassium, magnesium, and calcium, and metal salts.
  • a hydroxymethyl compound can be produced by subjecting a hydroformylation reaction product obtained by the above hydroformylation reaction to a hydrogenation reaction.
  • the hydrogenation reaction may be carried out by reacting a reducing reagent that generates hydride such as sodium borohydride with a hydroformylation reaction product, etc., but industrially, hydrogen gas and a hydroformylation reaction product in the presence of a catalyst, etc. It is advantageous to react with Although it does not specifically limit as a catalyst used when hydrogen gas, a hydroformylation reaction material, etc. are made to react, A well-known catalyst can be used. For example, those containing one or more elements selected from Group 6-12 transition metals in the periodic table of elements are preferable.
  • Raney metals such as Raney nickel, Raney cobalt and Raney copper, reduced nickel supported catalysts, reduction Cobalt-supported catalyst, copper-chromium oxide catalyst, copper-zinc oxide catalyst, copper-iron oxide catalyst, palladium black, platinum black, ruthenium black, palladium-supported silica, palladium-supported alumina, palladium-supported activated carbon, platinum Examples include supported silica, platinum-supported alumina, platinum-supported activated carbon, ruthenium-supported silica, ruthenium-supported alumina, ruthenium-supported activated carbon, rhodium-supported activated carbon, iridium-supported activated carbon, and rhenium-supported activated carbon.
  • the amount of the catalyst used when the hydrogen gas is reacted with the hydroformylation reaction product is not particularly limited, but can be appropriately selected depending on the type of catalyst and the reaction type.
  • the hydrogen gas used when reacting the hydrogen gas with the hydroformylation reaction product or the like may be diluted with a gas inert to the reaction, for example, nitrogen, helium, argon or the like and supplied to the reaction system.
  • a gas inert for example, nitrogen, helium, argon or the like and supplied to the reaction system.
  • the hydrogen pressure is not particularly limited, but is usually in the range of 0.1 to 20 MPaG, preferably 0.3 to 10 MPaG, more preferably 0.5 to 7 MPaG.
  • the hydrogenation reaction can be carried out without using a solvent, but a solvent can also be used.
  • the solvent is not particularly limited as long as it dissolves a hydroxymethyl form and a formyl form.
  • alcohols such as ethanol, isopropyl alcohol, butanol, 2-ethylhexanol and 2-octanol
  • esters such as butyl acetate and cyclohexyl acetate
  • decane dodecane
  • Saturated aliphatic hydrocarbons such as tetradecane
  • cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane, cyclododecane
  • aromatic hydrocarbons such as benzene, toluene, xylene, alkylnaphthalene
  • ethers such as dibutyl ether and tetrahydrofuran.
  • the temperature of the hydrogenation reaction can be appropriately set in consideration of the reaction rate and yield depending on the type and amount of catalyst used, but is usually 30 to 250 ° C., preferably 50 to 200 ° C., more preferably 70 to It is in the range of 170 ° C.
  • the reaction mode of the hydrogenation reaction is not particularly limited, and the hydrogenation reaction can be carried out either batchwise using a known reaction apparatus or continuous. Specifically, it can be carried out in any of a stirring reaction tank, a tower reaction tank, and a tubular reaction tank.
  • the mixture containing the hydroxymethyl compound obtained after completion of the hydrogenation reaction can be purified by a known method to isolate the hydroxymethyl compound.
  • the purity of the isolated hydroxymethyl compound is preferably 80 area% to 100 area%, more preferably 90 area% to 100 area%, and even more as the purity when analyzed by gas chromatography with a flame ion detector. Preferably, it is in the range of 95 area% to 100 area%.
  • a purification method in the case of purifying by a known method, for example, methods such as adsorption, extraction, neutralized water washing, distillation, crystallization and the like can be used, and these methods can be used in appropriate combination.
  • the production method of the present invention it is possible not only to produce a hydroxymethyl form and a formyl form from a raw material olefin in a high yield, but also to produce a specific stereoisomer with high selectivity.
  • the raw material olefin it is more preferable to use the compound (2) from the viewpoint of availability.
  • the hydroxymethyl compound obtained by the production method of the present invention can be reacted with an unsaturated fatty acid or derivative thereof, glycidyl halide, vinyl ether, vinyl ester, alkyne, or the like to form a polymerizable monomer. It can be used as a raw material for polymers such as (meth) acrylic acid esters, epoxy resins, and polyvinyl ethers.
  • the unsaturated fatty acid or derivative thereof include acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, methyl acrylate, methyl methacrylate, etc.
  • specific examples of the glycidyl halide include epichlorohydrin, epi Bromohydrin, 2-chloromethyl-3-methyloxirane, 2-chloromethyl-2-methyloxirane, etc.
  • Specific examples of the vinyl ether include butyl vinyl ether, halogenated alkyl vinyl ether, etc.
  • Specific examples of the vinyl ester Is vinyl acetate and the like, and specific examples of the alkyne are acetylene and the like.
  • (meth) acrylic acid ester can be carried out in accordance with, for example, the method described in JP-A-2001-139638, but is not limited thereto.
  • the production of glycidyl ether can be carried out in accordance with, for example, the method described in Japanese Patent No. 5249549, but is not limited thereto.
  • the production of vinyl ether can be carried out according to the method described in, for example, JP-A-2005-23049, but is not limited thereto.
  • the polymerization of the polymerizable monomer that can be produced from the hydroxymethyl compound obtained by the production method of the present invention can be carried out according to a known method.
  • Examples of the known method include, for example, JP-A-2005-255556, Examples include, but are not limited to, methods described in Japanese Patent No. 5951286, Japanese Patent Application Laid-Open No. 2009-79015, Japanese Patent No. 5249549, Japanese Patent No. 5009115, International Publication No. 2016/152310, etc. is not.
  • the composition range of the polymerizable monomer can be changed in an arbitrary range according to the performance required for the application.
  • the polymer obtained from the polymerizable monomer is low yellowing, heat resistance, low moisture absorption, transparency, light resistance, high refraction, low birefringence, mechanical properties, electrical properties, chemical properties, It is useful for optical materials, electrical / electronic materials, etc. because of its excellent processability and handling properties.
  • Applications using this polymer include information transmission medium applications such as plastic optical fibers, information recording medium applications such as optical disks, optical member applications such as optical lenses and optical films, optical semiconductors (LEDs, etc.), flat panel displays, etc.
  • Organic EL elements etc.
  • resin applications such as electronic circuits and optical circuits (optical waveguides)
  • resist material applications such as solder resists for printed circuit boards, color filters, printing inks, sealants, paints, coating agents, All electrical and electronic materials such as adhesives can be used.
  • Example 1 [Production of formyl body (hydroformylation reaction with rhodium catalyst)]
  • compound (2) manufactured by Tokyo Chemical Industry Co., Ltd.
  • 20 g of diisononyl phthalate manufactured by Jay Plus Co.
  • 0.0029 g (0.0112 mmol) of Rh (acac) (CO) 2 manufactured by NP Chemcat
  • Example 2 [Production of hydroxymethyl compound (hydrogenation reaction)]
  • 300 g (1.58 mol) of formyl body obtained in the same manner as in Example 1 150 g of isopropyl alcohol, and 6 g of reduced nickel-supported catalyst were placed, and the inside of the system was replaced with hydrogen.
  • the temperature in the system was adjusted to 150 ° C., and the internal pressure was adjusted to 5.0 MPaG.
  • the reaction was stopped after 4 hours while maintaining this temperature and pressure, and the reduced nickel-supported catalyst was removed by pressure filtration.
  • the solvent was distilled off from the resulting reaction solution to obtain 240.0 g of a hydroxymethyl compound.
  • the purity of the obtained hydroxymethyl compound was 97.5 area%, and the yield was 79.2% based on the formyl compound.
  • the component corresponding to the compound (1) having a retention time of 25.5 minutes was 99.8 area%.
  • Example 1 1 H-NMR (CDCl 3 , ⁇ 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)
  • NOESY-NMR the 11-position methylene hydrogen (1.26 ppm) and the hydroxymethylene group methylene hydrogen (3.38 ppm) and the 11-position methylene hydrogen (3.36 ppm) on the alicyclic structure of the compound (1) 1.26 ppm) and the interphase between 1-position and 6-position methine hydrogen (1.74-1.62 ppm) on the alicyclic structure were confirmed.
  • the formyl body obtained in Example 1 is a compound (3).
  • Example 3 [Integrated production of hydroxymethyl compounds (hydroformylation with rhodium catalyst)]
  • Compound (2) (Tokyo Chemical Industry Co., Ltd.) 200 g (1.25 mol), isopropyl alcohol 100 g, triphenyl phosphite (Kanto Chemical Co., Ltd.) 0.39 g (1.25 mmol), and Rh (acac) were added to a 500 ml autoclave. ) (CO) 2 (manufactured by NE Chemcat) 0.0032 g (0.0125 mmol) was added at room temperature, and the system was purged with nitrogen. The system was heated to 50 ° C. and stirred for 10 minutes while maintaining this temperature.
  • the reaction was stopped after 4 hours while maintaining this temperature and pressure, and the reduced nickel-supported catalyst was removed by pressure filtration to obtain a crude product containing a hydroxymethyl compound.
  • the crude product was distilled under reduced pressure at 150 ° C. and 1.4 kPa to remove low-boiling components.
  • the obtained distillation residue was subjected to thin-film distillation at 95 ° C. and 0.02 kPa to remove high boiling components, and 151.0 g of a hydroxymethyl compound was obtained.
  • the purity of the obtained hydroxymethyl compound was 97.9 area%, and the yield was 61.5% based on the compound (2).
  • the component corresponding to the compound (1) having a retention time of 25.5 minutes was 99.8 area%.
  • Example 4 [Integrated production of hydroxymethyl compounds (hydroformylation with cobalt catalyst)]
  • a glass flask having a capacity of 500 ml with the system being purged with nitrogen 76 g of an aqueous solution of NaCo (CO) 4 having a cobalt concentration of 0.7 wt%, 162.5 g of Compound (2) (manufactured by Tokyo Chemical Industry Co., Ltd.), and isononane (KH) 87.5 g (manufactured by Neochem) was added and stirred at room temperature to obtain a solution separated into two layers of an aqueous solution (lower layer) and an isononane solution of compound (2) (upper layer).
  • the obtained crude product containing the formyl body is transferred to an autoclave having a volume of 500 ml, charged with 2.6 g of a reduced nickel-supported catalyst, the system is replaced with hydrogen, and the pressure in the system is increased to 3.0 MPaG with hydrogen gas. Thereafter, the temperature in the system was adjusted to 150 ° C., and the internal pressure was adjusted to 5.0 MPaG. The reaction was stopped after 2 hours while maintaining this temperature and pressure, and the reduced nickel-supported catalyst was removed by pressure filtration. As a result of analyzing 201.0 g of the crude product containing the hydroxymethyl compound by gas chromatography, the purity of the hydroxymethyl compound containing the solvent was 36.3 area%, and the yield was based on the compound (2). Was 55.8%. As a result of analyzing the isomer ratio of the obtained hydroxymethyl compound by gas chromatography, the component corresponding to the compound (1) having a retention time of 25.5 minutes was 99.0 area%.
  • a reaction solution containing 1 7,10 ] -8-dodecene was obtained. Unreacted 5-norbornene-2-methanol and dicyclopentadiene were distilled off from the reaction solution at 125 ° C./3.0 kPa under reduced pressure to give 3-hydroxymethyltetracyclo [4.4.0.1 2,5 . 201 g of a crude product of 1 7,10 ] -8-dodecene was obtained. The resulting 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .
  • the purity of the obtained hydroxymethyl compound was 99.3 area%, and the yield was 14.4% based on 5-norbornene-2-methanol.
  • the component (isomer of compound (1)) having a retention time of 25.2 minutes was 55.0 area%, and the retention time was 25.9 minutes.
  • the component (isomer of compound (1)) was 43.0% by area.
  • Dodecane (3.6 g) was mixed with 0.018 g of t-butylperoxy-2-ethylhexanoate (LUPEROX26, manufactured by Arkema Yoshitomi Co., Ltd.) to obtain a monomer composition by stirring, and then the monomer composition Is poured into an aluminum cup with an inner diameter of 2.8 cm, heated in an oven at 100 ° C. for 3 hours and then at 120 ° C. for 1 hour in a nitrogen atmosphere, polymerized and molded, and then cooled to room temperature to form a transparent molded product Got.
  • Dodecane (2.0 g) was mixed with 0.01 g of t-butylperoxy-2-ethylhexanoate (LUPEROX26, manufactured by Arkema Yoshitomi), and a monomer composition was obtained by stirring. Is poured into a glass petri dish with an inner diameter of 5.0 cm, heated in an oven at 100 ° C. for 3 hours, then at 160 ° C. for 1 hour, polymerized and molded, and then cooled to room temperature to form a transparent molding I got a thing.
  • t-butylperoxy-2-ethylhexanoate (LUPEROX26, manufactured by Arkema Yoshitomi)
  • Glass transition temperature The molded product obtained by polymerization / molding method B was crushed into a granular or powder form, and about 10 mg of this was sampled as a test sample. The test sample was heated to 160 ° C.
  • the dried test piece was humidified in a constant temperature and humidity chamber with a temperature of 85 ° C. and a relative humidity of 85% for one week. After humidification, the moisture on the surface was wiped off and weighed (the weight at this time was defined as W). .
  • the water absorption was defined as (W ⁇ W0) / W0.
  • (4) Refractive Index / Abbe Number A test piece having a length of about 40 mm and a width of about 8 mm was cut from the molded product having a thickness of about 1 mm obtained by the polymerization / molding method B. With respect to the test piece, the refractive index n D at 23 ° C.
  • 3-hydroxymethyltetracyclo [4.4.0.1 2,5 .. which is a raw material for a polymer used in optical materials, electrical / electronic materials, and the like. It is possible to provide a method for producing [ 1,7,10 ] dodecane and the like with high yield and high selectivity to a specific stereoisomer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production de 3-hydroxyméthyltétracyclo[4. 4. 0. 12, 5. 17, 10]dodécane, qui consiste à soumettre du tétracyclo[4. 4. 0. 12, 5. 17, 10]-3-dodécane à une réaction d'hydroformylation et ensuite à une réaction d'hydrogénation ; et analogues.
PCT/JP2019/017681 2018-04-25 2019-04-25 Procédé de production d'alcool alicyclique et d'aldéhyde WO2019208710A1 (fr)

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JPH0570386A (ja) * 1991-09-11 1993-03-23 Kuraray Co Ltd 縮合環含有化合物
JPH0597769A (ja) * 1991-10-02 1993-04-20 Kuraray Co Ltd 縮合環含有化合物およびその製造方法
WO2015147242A1 (fr) * 2014-03-28 2015-10-01 三菱瓦斯化学株式会社 Composé bifonctionnel possédant un squelette de norbornane et son procédé de production
JP2015199919A (ja) * 2014-04-03 2015-11-12 三井化学株式会社 オレフィン重合用触媒、およびオレフィン重合体の製造方法
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US4391284A (en) * 1982-03-02 1983-07-05 International Flavors & Fragrances Inc. Use in modifying smoking tobacco aroma and flavor or mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives
JPH0570386A (ja) * 1991-09-11 1993-03-23 Kuraray Co Ltd 縮合環含有化合物
JPH0597769A (ja) * 1991-10-02 1993-04-20 Kuraray Co Ltd 縮合環含有化合物およびその製造方法
WO2015147242A1 (fr) * 2014-03-28 2015-10-01 三菱瓦斯化学株式会社 Composé bifonctionnel possédant un squelette de norbornane et son procédé de production
JP2015199919A (ja) * 2014-04-03 2015-11-12 三井化学株式会社 オレフィン重合用触媒、およびオレフィン重合体の製造方法
WO2016052370A1 (fr) * 2014-09-30 2016-04-07 三菱瓦斯化学株式会社 Résine de polycarbonate et lentille optique
WO2016153018A1 (fr) * 2015-03-25 2016-09-29 三菱瓦斯化学株式会社 Composé bifonctionnel possédant un squelette de norbornane et son procédé de production

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