Method for manufacturing diethanol compounds with a norbornene skeleton

Abstract

A method for manufacturing a target compound represented by the following formula (1), wherein the manufacturing method comprises a step (A) of supplying a mixture containing a raw material compound represented by the following formula (2) and a solvent to a hydrogenation reduction process in the presence of a catalyst having hydrogenation capability, wherein the solvent is a straight-chain or branched secondary or tertiary alcohol, wherein in the formula (1), R represents H, CH3 or C2H5, and in the formula (2), R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7, or C4H9.

Description

Technical Field

[0001] This invention relates to a method for manufacturing diethanol compounds having a norbornene skeleton. Background Technology

[0002] Diethanol compounds with a norbornene skeleton are known to exhibit excellent characteristics when used as adhesives or resin raw materials. As a method for manufacturing diethanol compounds with a norbornene skeleton, for example, Patent Document 1 describes obtaining diethanol compounds with a norbornene skeleton by hydrogenation of the corresponding ester compound.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2015 / 147242 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] Hydrogenation reactions are typically carried out by reacting an ester-containing compound with hydrogen gas using a catalyst containing copper oxide and a reaction solvent. In Patent Document 1, the ester compound of the substrate, toluene solvent, and copper oxide catalyst were added, and the reaction was carried out at a reaction temperature of 215°C, a reaction pressure of 10 MPa, and a reaction time of 8 hours. However, the amount of catalyst used was 20 wt% relative to the substrate, and the amount of toluene solvent used was 300 wt% relative to the substrate. In addition, the generated diethanol compound had low solubility in toluene solvent, and it was determined that a paste-like product of catalyst, diethanol compound, and unreacted ester compound precipitated in toluene solvent. In this case, dilution with methanol solvent was performed after the reaction, thereby enabling catalyst filtration separation. However, it was determined that in the reaction solution, apart from the diethanol compound, which is the target compound, about 1% of the intermediate ester compound remained. When the target compound is used as a polymer feedstock, the intermediate of the target compound may tend to hinder the reaction. In addition, both the target compound and the intermediate are high in viscosity and high in boiling point, making it difficult to separate them by single distillation or thin-film distillation. In addition, high-stage distillation purification was considered to separate the intermediate from the target compound, but this resulted in a deterioration in yield, making it difficult to call an economical method.

[0008] Therefore, there is room for improvement in the technology of Patent Document 1 from the viewpoint of suppressing the generation of intermediates.

[0009] On the other hand, while using alcohol solvents can solve the problem of precipitation of paste-like products in solvents, in the case of methanol and ethanol, the high reaction temperature during hydrogenation results in partial pressure, leading to a lower concentration of hydrogen in the gas phase and thus a tendency for the reaction time to be longer. Therefore, it is difficult to say that this is an economical method.

[0010] Furthermore, Patent Document 1 clarified that while using cyclohexanol as a solvent can avoid the decrease in hydrogen concentration as described above, a portion of it undergoes transesterification with the intermediate, easily generating transesterification products as byproducts in the reaction solution. In this case, similar to the aforementioned intermediate, there is a tendency to hinder the reaction with the polymer. Both the target compound and the byproducts are highly viscous and have high boiling points, making it difficult to separate the byproducts from the target compound using single distillation or thin-film distillation. Additionally, using high-stage distillation purification for the aforementioned separation deteriorates the yield, making it difficult to consider a cost-effective method.

[0011] Therefore, there is room for improvement in the technology of Patent Document 1 from the viewpoint of suppressing the generation of byproducts.

[0012] The present invention was made in view of the above-mentioned problems, and its object is to provide a method for manufacturing a diethanol compound, which can suppress the formation of intermediates and by-products in the manufacturing of diethanol compounds using hydrogenation reactions.

[0013] Technical solutions to the problem

[0014] The inventors discovered that, in the manufacture of diethanol compounds having a norbornene skeleton, the above-mentioned problems can be solved by using a specified alcohol as a solvent in the hydrogenation reaction, thus completing the present invention.

[0015] That is, the present invention is as follows.

[0016] [1] A method for manufacturing a target compound represented by the following formula (1), wherein the manufacturing method comprises a step (A) of supplying a mixture containing a raw material compound represented by the following formula (2) and a solvent to a hydrogenation reduction process in the presence of a catalyst having hydrogenation capability, wherein the solvent is a straight-chain or branched secondary or tertiary alcohol.

[0017]

[0018] (In the above formula (1), R represents H, CH3 or C2H5,)

[0019]

[0020] (In the above formula (2), R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7 or C4H9.)

[0021] [2] According to the manufacturing method described in [1], the boiling point of the solvent is 100 to 230°C.

[0022] [3] According to the manufacturing method described in [1] or [2], wherein the solvent is represented by the following formula (a),

[0023]

[0024] (In formula (a) above, R1 represents H or CH3, R2 represents CH3, C2H5, C3H7 or C4H9, and R3 represents C3H7, C4H9, C5H) 11 C6H 13 C7H 15 C8H 17 C9H 19 C 10 H 21 C 11 H 23 Or C 12 H 25 。 )

[0025] [4] The manufacturing method according to any one of [1] to [3], wherein the content of the intermediate represented by the following formula (3) in the target compound is 0.5% by mass or less.

[0026]

[0027] (In the formula, R represents H, CH3, or C2H5, and R1 represents CH3, C2H5, C3H7, or C4H9.)

[0028] [5] The manufacturing method according to any one of [1] to [4], wherein the content of the byproduct represented by the following formula (4) in the target compound is less than 0.5% by mass.

[0029]

[0030] (In the formula, R represents H, CH3 or C2H5, and R2 represents C4H9 or C5H) 11 C6H 13 C7H 15 C8H 17 C9H 19 C 10 H 21 C 11 H 23 C 12 H 25 C 13 H 27 C14 H 29 。 )

[0031] [6] The manufacturing method according to any one of [1] to [5], wherein the solvent is 2-octanol and / or tetrahydrolinalool.

[0032] [7] The manufacturing method according to any one of [1] to [6], wherein in the step (A), the catalyst is activated at a first temperature and a first pressure, and after the activation, the raw material compound is hydrogenated at a second temperature and a second pressure.

[0033] [8] According to the manufacturing method described in [7], wherein the second pressure exceeds 5 MPa and is less than 20 MPa.

[0034] [9] The manufacturing method according to [7] or [8], wherein the second pressure exceeds 5 MPa and is less than 8 MPa.

[0035]

[10] According to the manufacturing method described in [9], wherein the solvent is a straight-chain or branched tertiary alcohol.

[0036]

[11] According to the manufacturing method described in

[10] , wherein the solvent is tetrahydrolinalool.

[0037] Invention Effects

[0038] According to the manufacturing method of the present invention, a method is provided that can suppress both the formation of intermediates and the formation of byproducts in the manufacture of diethanol compounds utilizing hydrogenation reactions. Detailed Implementation

[0039] Hereinafter, a detailed description will be given of a method for carrying out the present invention (hereinafter also referred to as "this embodiment"). This embodiment is illustrative of the present invention and is not intended to limit the invention to its following content. The present invention can be implemented with appropriate modifications within its scope.

[0040] <Method for manufacturing diethanol compounds with a norbornene skeleton>

[0041] The manufacturing method of this embodiment is a method for manufacturing a target compound represented by the following formula (1) (i.e., a diethanol compound having a norbornene skeleton represented by the above formula (1), hereinafter also simply referred to as the "target compound"), comprising a step (A) of supplying a mixture containing a raw material compound represented by the following formula (2) and a solvent to a hydrogenation reduction process in the presence of a catalyst with hydrogenation capability, wherein the solvent is a straight-chain or branched secondary or tertiary alcohol.

[0042]

[0043] (In formula (1) above, R represents H, CH3 or C2H5.)

[0044]

[0045] (In the above formula (2), R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7 or C4H9.)

[0046] The manufacturing method of this embodiment is configured as described above, thus suppressing both the formation of intermediates and byproducts in the production of diethanol compounds based on hydrogenation reactions. This target compound is preferably used as a coating additive, adhesive, resin raw material, etc.

[0047] The synthetic route for producing the target compound is not limited to the following. For example, dicyclopentadiene or an olefin having cyclopentadiene and functional groups can be used as the starting material, and the synthetic route represented by the following formula (I) can be adopted.

[0048]

[0049] In formula (I) above, R represents H, CH3, or C2H5; R1 represents CH3, C2H5, C3H7, or C4H9; and R2 represents an organic group in a straight-chain or branched secondary or tertiary alcohol, preferably C4H9 or C5H9. 11 C6H 13 C7H 15 C8H 17 C9H 19 Or C 10 H 21 。 )

[0050] Formula (3) in Formula (I) above represents a synthetic intermediate that may accompany the target compound. Hereinafter, for ease of explanation, this synthetic intermediate will also be simply referred to as "intermediate". In addition, Formula (4) in Formula (I) above represents a byproduct that may accompany the target compound. Hereinafter, for ease of explanation, it will also be simply referred to as "byproduct".

[0051] [Monoolefins with 14 to 19 carbon atoms represented by formula (5)]

[0052] In this embodiment, a monoolefin with 14 to 19 carbon atoms, represented by the following formula (5), can be produced by carrying out a Diels-Alder reaction of an olefin with a functional group with dicyclopentadiene.

[0053]

[0054] (In formula (5), R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7 or C4H9.)

[0055] Examples of alkenes having functional groups for the Diels-Alder reaction are not particularly limited and include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc., with methyl methacrylate, ethyl methacrylate, and methyl acrylate being preferred.

[0056] In this embodiment, the dicyclopentadiene used in the Diels-Alder reaction is preferably high-purity dicyclopentadiene, and more preferably dicyclopentadiene with low content of impurities such as butadiene and isoprene. The purity of the dicyclopentadiene is preferably 90% or more, more preferably 95% or more. In addition, it is known that dicyclopentadiene depolymerizes into cyclopentadiene (so-called monocyclopentadiene) under heating conditions, so cyclopentadiene can also be used instead of dicyclopentadiene. It should be noted that the monoolefins with 14 to 19 carbon atoms represented by the above formula (5) are essentially generated via monoolefins with 9 to 14 carbon atoms represented by the following formula (6) (the product of the first stage Diels-Alder reaction). It is believed that the monoolefins generated by the following formula (6) exist as new parent dienes in the cyclopentadiene and the Diels-Alder reaction (the second stage Diels-Alder reaction) present in the reaction system, generating monoolefins with 14 to 19 carbon atoms represented by the above formula (5).

[0057]

[0058] (In formula (6), R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7 or C4H9.)

[0059] The presence of cyclopentadiene in the reaction system promotes the efficient conduction of the aforementioned two-stage Diels-Alder reaction. Therefore, the preferred reaction temperature for the Diels-Alder reaction is 100°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. On the other hand, to suppress the production of high-boiling byproducts, the reaction is preferably carried out at a temperature below 250°C. Furthermore, hydrocarbons, alcohols, esters, etc., can be used as reaction solvents; aliphatic hydrocarbons with 6 or more carbon atoms, cyclohexane, toluene, xylene, ethylbenzene, mesitylene, propanol, butanol, etc., are preferred.

[0060] As for the above-mentioned Diels-Alder reaction, various reaction methods can be adopted, such as batch reaction based on a trough reactor, semi-batch reaction with substrate supplied to a trough reactor under reaction conditions, and continuous flow reaction in a tubular reactor under reaction conditions.

[0061] The reaction product obtained by the Diels-Alder reaction described above (a monoolefin with 14 to 19 carbon atoms represented by formula (5) above) can also be used directly as a raw material for the subsequent hydroformylation reaction, or it can be purified by methods such as distillation, extraction, or crystallization before being supplied to the next process. It should be noted that the monoolefin with 14 to 19 carbon atoms represented by formula (5) above is not limited to the substance synthesized as described above, and can also be used in the manufacturing method of this embodiment as long as it is available as a commercially available product.

[0062] [The raw material compound represented by formula (2)]

[0063] The raw material compound represented by formula (2) in the above formula (I) can be produced, for example, by hydroformylation of a monoolefin with 14 to 19 carbon atoms represented by formula (5) with carbon monoxide and hydrogen in the presence of a rhodium compound and an organophosphorus compound.

[0064] The rhodium compound used in the above hydroformylation reaction is not particularly limited; for example, compounds that form complexes with organophosphorus compounds and exhibit hydroformylation activity in the presence of carbon monoxide and hydrogen can be used. Rhodium dicarbonylacetylacetone (hereinafter also referred to as "Rh(acac)(CO)2"), Rh2O3, and Rh4(CO) can also be used. 12 Rh6(CO) 16 Catalyst precursors such as Rh(NO3)3 are introduced into the reaction mixture along with organophosphorus compounds to form a catalytically active rhodium metal hydride carbonyl phosphorus complex within the reaction vessel. Alternatively, the rhodium metal hydride carbonyl phosphorus complex can be prepared in advance and introduced into the reactor. In this embodiment, it is preferable to react Rh(acac)(CO)2 with the organophosphorus compound in the presence of a solvent, and then introduce it into the reactor along with excess organophosphorus compound to form a catalytically active rhodium-organophosphorus complex for the hydroformylation reaction.

[0065] The amount of rhodium compound used in the above-mentioned hydroformylation reaction is preferably 0.1 to 60 micromoles, more preferably 0.1 to 30 micromoles, further preferably 0.2 to 20 micromoles, and even more preferably 0.5 to 10 micromoles, relative to 1 mole of a monoolefin with 14 to 19 carbon atoms represented by formula (5) that serves as the substrate for the hydroformylation reaction. By making the amount of rhodium compound used less than 60 micromoles relative to 1 mole of a monoolefin with 14 to 19 carbon atoms, the cost of rhodium catalyst can be reduced even without the installation of a rhodium complex recycling and reuse device, thus reducing the economic burden associated with recycling and reuse equipment.

[0066] In the above-described hydroformylation reaction, the organophosphorus compound used as a catalyst for forming the rhodium compound and the hydroformylation reaction can be phosphine represented by the general formula P(-R1)(-R2)(-R3) or phosphite represented by P(-OR1)(-OR2)(-OR3). Specific examples of R1, R2, and R3 in the above general formulas include aryl groups that can be substituted with alkyl or alkoxy groups having 1 to 4 carbon atoms, and alicyclic alkyl groups that can be substituted with alkyl or alkoxy groups having 1 to 4 carbon atoms. Triphenylphosphine and triphenyl phosphite are preferred. The amount of organophosphorus compound used relative to the rhodium atoms in the rhodium compound is preferably 300 to 10,000 moles, more preferably 500 to 10,000 moles, further preferably 700 to 5,000 moles, and even more preferably 900 to 2,000 moles. When the amount of organophosphorus compound used is 300 moles or more of rhodium atoms, the rhodium metal hydride carbonyl phosphorus complex of the catalyst active material tends to function stably, resulting in a tendency for improved reaction efficiency. Furthermore, when the amount of organophosphorus compound used is less than 10,000 moles of rhodium atoms, there is a tendency for improved economic efficiency from the perspective of the cost of organophosphorus compounds.

[0067] The above-described hydroformylation reaction can also be carried out without a solvent, but it is preferable to use a reaction-inert solvent. As a solvent, there is no particular limitation as long as it is a solvent capable of dissolving monoolefins with 14 to 19 carbon atoms represented by formula (5), dicyclopentadiene or cyclopentadiene, the aforementioned rhodium compound, or the aforementioned organophosphorus compound. Specifically, examples include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; esters such as aliphatic esters, alicyclic esters, and aromatic esters; alcohols such as aliphatic alcohols and alicyclic alcohols; and aromatic halides. Among these, hydrocarbons are preferred, and among these hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferred.

[0068] The preferred temperature for the above hydroformylation reaction is 40°C to 160°C, more preferably 80°C to 140°C. At a reaction temperature of 40°C or higher, a sufficient reaction rate can be obtained, suppressing the residual mono-olefin as a starting material. Furthermore, by keeping the reaction temperature below 160°C, there is a tendency to suppress the formation of byproducts from the starting mono-olefin and the reaction products, preventing a decrease in reaction yield.

[0069] In the above-described hydroformylation reaction, the reaction is carried out under pressure using carbon monoxide (hereinafter also referred to as "CO") and hydrogen (hereinafter also referred to as "H2") gases. CO and H2 gases can be introduced into the reaction system independently or as a pre-prepared mixed gas. The molar ratio of CO to H2 gases introduced into the reaction system (=CO / H2) is preferably 0.2 to 5, more preferably 0.5 to 2, and even more preferably 0.8 to 1.2. When the molar ratio of CO to H2 gases is within the above range, there is a tendency to increase the reactivity of the hydroformylation reaction and the selectivity of the target aldehyde. It should be noted that the amount of CO and H2 gases introduced into the reaction system decreases as the reaction proceeds; therefore, if a pre-prepared mixed gas of CO and H2 is used, the reaction control is sometimes simpler.

[0070] The reaction pressure for the above-mentioned hydroformylation reaction is preferably 1 to 12 MPa, more preferably 1.2 to 8 MPa, and even more preferably 1.5 to 5 MPa. By setting the reaction pressure to 1 MPa or higher, a sufficient reaction rate is easily obtained, and there is a tendency to suppress the residue of the monoolefin used as a raw material. Furthermore, by setting the reaction pressure to 12 MPa or lower, expensive equipment with excellent pressure resistance is not required, thus offering an economic advantage. In particular, when the reaction is carried out in a batch or semi-batch manner, since CO and H2 gases are discharged and the pressure is reduced after the reaction, the lower the pressure, the less CO and H2 gases are lost, thus offering an economic advantage.

[0071] The preferred reaction mode for the above hydroformylation reaction is a batch reaction or a semi-batch reaction. The semi-batch reaction can be carried out as follows: a rhodium compound, an organophosphorus compound, and the above-mentioned solvent are added to the reactor, and the reactor is pressurized and heated based on CO / H2 gas, etc., as described in the reaction conditions. Then, the monoolefin or its solution as a raw material is supplied to the reactor.

[0072] The reaction product obtained in the above hydroformylation reaction can also be used directly as a raw material for the next reduction reaction. For example, it can be purified by distillation, extraction, crystallization, etc., and then supplied to the next process. It should be noted that the raw material compound represented by the above formula (2) is not limited to the compound synthesized as described above. As long as it can be obtained as a commercially available product, it can also be used in the manufacturing method of this embodiment.

[0073] [Process (A)]

[0074] The manufacturing method of this embodiment includes a step (A) of hydrogenation reduction in which a mixture containing a raw material compound represented by the above formula (2) and a solvent is supplied in the presence of a catalyst with hydrogenation capability (hereinafter also referred to as a "hydrogenation catalyst"). In this embodiment, a straight-chain or branched secondary or tertiary alcohol is used as the solvent in this step (A). By using this solvent, not only can the target compound be obtained from the raw material compound, but the formation of intermediates and by-products can also be suppressed. The reason why the formation of intermediates and by-products can be suppressed by using the solvent in this embodiment is not necessarily clear, but it is predicted as follows. That is, it is believed that if it is a straight-chain or branched secondary alcohol and / or tertiary alcohol, due to the moderate steric hindrance, it is difficult to produce transesterification reaction that causes by-products, and even if it does, it is easy to become the target product through subsequent hydrogenation. However, the mechanism of action of this embodiment is not limited to the above.

[0075] In step (A), using straight-chain or branched secondary alcohols and / or tertiary alcohols as solvents is crucial in the reduction reaction of this embodiment. In hydrogenation reactions, assuming the use of aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, the resulting diethanol compound is difficult to dissolve in the solvent, tending to precipitate as a paste-like product of catalyst, diethanol compound, and unreacted ester compound in the solvent. While using alcohol solvents can solve the problem of the paste-like product, using primary alcohols such as methanol or ethanol as solvents for hydrogenation results in a lower hydrogen concentration in the gas phase due to the high reaction temperature, leading to a longer reaction time. Furthermore, the inventors have found that, for example, using cyclohexanol, a cyclic alcohol, while eliminating the problems of the paste-like product and the low hydrogen concentration in the gas phase, a portion of the hydrogen undergoes transesterification with the ester compound, tending to leave approximately 1% of transesterification product in the hydrogenation reaction solution. In contrast, hydrogenation using straight-chain or branched secondary alcohols and / or tertiary alcohols as solvents can solve the problems of pasty products, low hydrogen concentration in the gas phase, and residual transesterification products of more than 1%.

[0076] There are no particular limitations on whether they are straight-chain or branched secondary and / or tertiary alcohols. Examples of secondary alcohols include 2-octanol, 2-nonanol, 2-decanol, 4-decanol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 2-dodecanol, 2-tridecanol, and 2-tetradecanol; and tertiary alcohols include tetrahydrolinalool, 3-methyl-3-heptanol, 3-ethyl-3-pentanol, 4-methyl-4-heptanol, 3,4-dimethyl-3-hexanol, 3,5-dimethyl-3-hexanol, and 3-ethyl-2-methyl-3-pentanol.

[0077] In this embodiment, from the viewpoint of more effectively suppressing the formation of intermediates and byproducts, the boiling point of the solvent is preferably 100–230°C, more preferably 140–220°C, and even more preferably 160–200°C. The boiling point is a known value of the solvent at room temperature and pressure.

[0078] In this embodiment, from the viewpoint of more effectively suppressing the formation of intermediates and byproducts, the solvent is preferably represented by the following formula (a).

[0079]

[0080] (In formula (a) above, R1 represents H or CH3, R2 represents CH3, C2H5, C3H7 or C4H9, and R3 represents C3H7, C4H9, C5H) 11 C6H 13 C7H 15 C8H 17 C9H 19 C 10 H 21 C 11 H 23 Or C 12 H 25 。 )

[0081] Among them, solvents such as 2-octanol and tetrahydrolinalool are particularly preferred.

[0082] The hydrogenation catalyst used in step (A) is not limited to the following, and examples include catalysts containing at least one element selected from copper, chromium, iron, zinc and aluminum. Among them, copper-based catalysts such as Cu-Cr catalysts, Cu-Zn catalysts, Cu-Zn-Al catalysts and Cu-Fe-Al catalysts are preferred, and Cu-Cr catalysts and Cu-Zn-Al catalysts are more preferred.

[0083] The amount of hydrogenation catalyst used is not particularly limited, but is preferably 1 to 50% by mass relative to the raw material compound represented by formula (2) as the substrate. When the amount of hydrogenation catalyst is 1% by mass or more, the reaction proceeds fully, and the yield of the target product tends to increase. However, even if the amount of hydrogenation catalyst is set to more than 50% by mass, there is a tendency that the increase in reaction rate corresponding to the amount of catalyst supplied to the reaction cannot be obtained. Therefore, from an economic point of view, it is preferable to set the amount to 50% by mass or less. That is, by setting the amount of hydrogenation catalyst in the above range, there is a tendency to effectively carry out the hydrogenation reaction. From the above point of view, the amount of hydrogenation catalyst is more preferably 2 to 20% by mass, and more preferably 5 to 10% by mass.

[0084] In this embodiment, from the viewpoint of further improving reaction efficiency, it is preferable to activate the catalyst at a first temperature and a first pressure in step (A), and then hydrogenate the feedstock compound at a second temperature and a second pressure after activation. It should be noted that, as mentioned above, the byproduct water is considered to deactivate the activated hydrogenation catalyst; therefore, it is preferable to remove the water before hydrogenation.

[0085] Activation of the hydrogenation catalyst is an operation used to reduce the hydrogenation catalyst, which can be carried out at a first temperature and a first pressure.

[0086] In this embodiment, the first temperature is preferably 100°C or higher and 170°C or lower. When the first temperature is 170°C or lower, there is a tendency to suppress the occurrence of side reactions and decomposition reactions. In addition, when the first temperature is 100°C or higher, there is a tendency for the reduction reaction of the catalyst to be completed in a reasonable amount of time. From the same viewpoint, the first temperature is more preferably 120°C or higher and 170°C or lower.

[0087] In this embodiment, the first pressure is preferably 0.5 MPa or more and 5 MPa or less. When the first pressure is 0.5 MPa or more, there is a tendency to obtain a sufficient reaction rate; when it is 5 MPa or less, the loss of H2 gas during water removal is reduced, which is therefore economically advantageous. From the same viewpoint, the first pressure is more preferably 1 MPa or more and 3 MPa or less, and even more preferably 1.5 MPa or more and 2 MPa or less.

[0088] In this embodiment, the reaction time for activating the hydrogenation catalyst is preferably 0.2 hours or more and 3 hours or less. When the first reaction time is 0.2 hours or more, there is a tendency for the catalyst to be in a better reduced state, while when the first reaction time is 3 hours or less, there is a tendency for the reduction reaction of the catalyst to proceed sufficiently and for the reaction time to be reduced.

[0089] The activation of the hydrogenation catalyst can be carried out in the absence of the feedstock compound, but in this embodiment, from the viewpoint of reaction efficiency, it is preferable to carry it out in the presence of the feedstock compound. When the activation of the hydrogenation catalyst is carried out in the presence of the feedstock compound, water is produced as a byproduct as reducing water. There are no particular limitations on the operation for removing such water; for example, any method can be used, such as purging the gas phase several times to remove water present in the gas phase from the reaction system, or pre-installing a nozzle line in the mixture to bubble an inert gas such as H2 or N2 to remove water from the reaction system. As for determining whether the treatment is complete, a method can be used to install a trap at the exhaust end and continue operation based on an assumed amount of water of 2 to 3 times, or a method can be used to measure the water content in the reaction solution.

[0090] Hydrogenation of the feedstock compound is an operation used to obtain the target compound, and can be carried out at a second temperature and a second pressure.

[0091] In this embodiment, the second temperature is preferably above 170°C and below 250°C. When the second temperature is below 250°C, there is a tendency to suppress side reactions and decomposition reactions, and to obtain the target compound in high yield. Furthermore, when the second temperature exceeds 170°C, there is a tendency for the reaction to complete in a reasonable time, and there is a tendency to avoid a decrease in productivity and a decrease in the yield of the target product. From the same viewpoint, the second temperature is more preferably above 190°C and below 230°C.

[0092] In this embodiment, the second pressure is preferably greater than 5 MPa and less than 20 MPa. When the second pressure is less than 20 MPa, there is a tendency to suppress side reactions and decomposition reactions, and to obtain the target compound in high yield. In addition, when the second pressure exceeds 5 MPa, there is a tendency for the reaction to be completed in a reasonable time. From the same point of view, it is more preferable to exceed 5 MPa and less than 15 MPa, and even more preferable to exceed 5 MPa and less than 12 MPa.

[0093] It should be noted that, in terms of the design of the reaction apparatus (equipment cost), it is preferable to implement a process that can reduce the hydrogenation pressure. From this point of view, the second pressure is preferably 8 MPa or less, more preferably more than 5 MPa but less than 8 MPa. Under such conditions, the reaction time tends to be longer. Here, if the reaction temperature is increased in order to shorten the reaction time, there is a tendency for the formation of intermediates and by-products to increase. However, in such cases, the formation of intermediates and by-products can be significantly reduced by using the solvent in this embodiment. In this embodiment, from the viewpoint of more effectively reducing the formation of intermediates and by-products when the second pressure is set to 8 MPa or less, a straight-chain or branched tertiary alcohol is preferably used as the solvent in step (A), and tetrahydrolinalool is particularly preferred. Based on the above viewpoints, in this embodiment, when using tetrahydrolinalool as a solvent, the second pressure is preferably greater than 5 MPa and less than 8 MPa, and the second temperature is preferably greater than 215°C and less than 250°C. From the viewpoint of further reducing the reaction time, when using tetrahydrolinalool as a solvent, the second pressure is preferably greater than 5 MPa and less than 8 MPa, and the second temperature is more preferably greater than 220°C and less than 250°C.

[0094] It should be noted that in the hydrogenation of this embodiment, an inert gas (such as nitrogen or argon) may also coexist in the hydrogenation reaction.

[0095] In addition, the pressure mentioned above refers to the value as the partial pressure of hydrogen.

[0096] In this embodiment, from the viewpoint of the physical properties obtained when further processing the target compound, the content of the intermediate represented by the above formula (3) in the target compound obtained in step (A) of this embodiment is preferably 0.5% by mass or less. The content of the above intermediate can be determined based on the method described in the examples described later. In addition, the content of the above intermediate can be adjusted to the above range by using straight-chain or branched secondary alcohols and / or tertiary alcohols in step (A).

[0097] In this embodiment, from the viewpoint of the physical properties obtained when further processing the target compound, the content of the byproduct represented by the above formula (4) in the target compound obtained in step (A) of this embodiment is preferably 0.5% by mass or less. The content of the above intermediate can be determined based on the method described in the examples described later. In addition, the content of the above intermediate can be adjusted to the above range by using straight-chain or branched secondary alcohols and / or tertiary alcohols in step (A).

[0098] The target compound obtained in step (A) of this embodiment can be purified, for example, by distillation, extraction, crystallization, etc.

[0099] Example

[0100] The following embodiments will be described in more detail, but the embodiments are not limited to these embodiments.

[0101] <Analytical Methods>

[0102] (1) Determination conditions for gas chromatography analysis

[0103] Analytical apparatus: Shimadzu Corporation GC-2010Plus capillary gas chromatograph

[0104] Analytical column 1: InertCap1 (30m, 0.32mmI.D., film thickness 0.25μm) manufactured by GL Science Co., Ltd.

[0105] Column oven temperature 1: 60℃ (0.5 minutes) - 15℃ / minute - 280℃ (4 minutes)

[0106] Detector 1: FID, temperature 280℃

[0107] Internal standard: p-xylene

[0108] Analytical column 2: InertCapWAX (30m, 0.32mmI.D., film thickness 0.25μm) manufactured by GL Science Co., Ltd.

[0109] Column oven temperature 2: 60℃ (0.5 min) - 20℃ / min - 250℃ (20 min)

[0110] Detector 2: FID, temperature 250℃

[0111] (2) GC-MS determination conditions

[0112] Analytical device: manufactured by Shimadzu Corporation, GCMS-QP 2010Plus

[0113] Ionization voltage: 70V

[0114] Analytical column: Agilent Technologies DB-1 (30 μm, 0.32 mm I.D., 1.00 μm film thickness)

[0115] Column oven temperature: 60℃ (0.5 minutes) - 15℃ / minute - 280℃ (4 minutes)

[0116] <Example 1>

[0117] (Obtaining monoolefins)

[0118] 215 g (2.50 mol) of methyl acrylate and 165 g (1.25 mol) of dicyclopentadiene were added to a 500 mL stainless steel reactor and reacted at 220 °C for 2 hours. A reaction solution containing 152 g of a monoolefin represented by formula (5a) was obtained, purified by distillation, and a portion of it was supplied to the subsequent reaction stage.

[0119]

[0120] (Obtaining aldehydes)

[0121] The hydroformylation of a monoolefin represented by formula (5a) was carried out in a 500 mL stainless steel reactor. 100 g of distilled and purified monoolefin represented by formula (5a), 96 g of 2-octanol (manufactured by Kokura Synthetic Industries), 213 mg of triphenyl phosphite (manufactured by Wako Pure Chemical Industries) (1500 mol ppm relative to the monoolefin), and 355 μg of Rh(acac)(CO)2 (manufactured by NEChemcat) (3 mol ppm relative to the monoolefin) were added to the reactor. After purging the reactor atmosphere three times with nitrogen and CO / H2 mixed gases, the system was pressurized with CO / H2 mixed gas, and the reaction was carried out at 100 °C and 2 MPa for 3 hours.

[0122] After the reaction was completed, the reaction solution was analyzed by gas chromatography and GC-MS. The results showed that the reaction solution containing 112.6 g of the starting compound represented by the following formula (2a) with a molecular weight of 248 was obtained as the main product (substrate conversion rate 100% (=(introduced monoolefin - residual introduced monoolefin) / introduced monoolefin)×100%), and the aldehyde yield was 99.5% (=main product / introduced monoolefin×100%).

[0123] Next, the starting compound represented by formula (2a) is purified by distillation, and a portion of it is supplied to the subsequent reaction.

[0124]

[0125] (Reduction by a catalyst)

[0126] 54.94 g of the distilled and purified raw material compound represented by formula (2a), 8.24 g of Cu-Zn-Al catalyst (manufactured by Nippon Kaisha Co., Ltd.: E-01X), and 120.86 g of 2-octanol (manufactured by Kokura Synthetic Industries) were added to a 300 mL stainless steel reactor equipped with a nitrogen bubbling nozzle. After three cycles of atmosphere replacement with nitrogen and H2 gas, the system was pressurized with H2 gas, and the catalyst was reduced at 150°C and 2 MPa for 1 hour. A trap was installed on the exhaust line, and while maintaining 150°C, the pressure was reduced to 0 MPa. A small amount of nitrogen gas was then flowed through the nitrogen bubbling nozzle to remove the reduced water from the reaction solution. The trap volume was 3.90 g.

[0127] (Dimethyl alcohol is obtained through hydrogenation)

[0128] Next, after three cycles of atmosphere replacement within the reactor using H2 gas, the system was pressurized with H2 gas, and the hydrogenation reaction was carried out at 215°C and 9.5 MPa. Specifically, 2-octanol was used as the solvent for the hydrogenation reaction. Samples were taken every 5 hours during the reaction.

[0129] The sample solution was diluted with acetone, and the catalyst was filtered through a membrane filter with a pore size of 0.2 μm. Gas chromatography and GC-MS were used to analyze the target compound (represented by formula (1a) with a molecular weight of 222), which was the main product. Quantitative analysis was also performed on an ester compound (intermediate) with a molecular weight of 250 (represented by formula (3a)) and an transesterification compound (byproduct) with a molecular weight of 349 (represented by formula (4a)). It should be noted that the quantitative analysis was performed using analytical column 2 (InertCapWAX). After 15 hours, the amount of the intermediate represented by formula (3a) was 0.45% (=intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100). Additionally, the amount of the byproduct represented by formula (4a) was 0.42% (=byproduct represented by formula (4a) / (all components other than 2-octanol and acetone) × 100).

[0130] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 47.46 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%) and the yield of the target compound was 96.50% (=target compound / starting compound×100%).

[0131] Furthermore, the reaction solution was purified by single distillation using a 300 mL three-necked flask equipped with a thermometer, an N2 bubbling nozzle, and a stir bar (it should be noted that the distillation stage was 1, the distillation temperature was 170–180 °C, and the vacuum degree was 2 torr). After purification, gas chromatography analysis was performed using analytical column 1 (InertCap 1), confirming that it contained 44.03 g of the main fraction of the target compound represented by formula (1a), 99.17% diethanol purity (= target compound represented by formula (1a) / (all components other than acetone) × 100)), and 92.00% distillation yield (= target compound obtained / target compound input × 100%). In addition, analytical column 2 (InertCap WAX) was used, and the amount of the intermediate represented by formula (3a) was 0.43% (= intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100). In addition, the amount of byproduct represented by formula (4a) is 0.40% (=byproduct represented by formula (4a) / (all components other than 2-octanol and acetone) × 100).

[0132]

[0133] <Comparative Example 1>

[0134] The hydrogenation reaction was carried out in the same manner as in Example 1, except that 1-octanol was used instead of 2-octanol as the solvent for the hydrogenation reaction. After 15 hours, the amount of the intermediate represented by formula (3a) was 0.47% (= intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100). In addition, the amount of the byproduct represented by formula (4b) was 4.23% (= byproduct represented by formula (4b) / (all components other than 2-octanol and acetone) × 100).

[0135] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 45.58 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%) and diethanol yield 92.67% (=target compound / starting compound×100%).

[0136] Furthermore, the reaction solution was purified by single distillation using a 300 mL three-necked flask equipped with a thermometer, an N2 bubbling nozzle, and a stir bar (note that the distillation stage was 1, the distillation temperature was 170–180 °C, and the vacuum degree was 2 torr). After purification, gas chromatography analysis was performed using column 1 (InertCap 1), and the results confirmed that the main fraction containing the target compound represented by formula (1a) was 40.49 g, the diethanol purity was 98.28% (=target compound represented by formula (1a) / (all components other than acetone) × 100)), and the distillation yield was 87.30% (=target compound obtained / target compound input × 100%). In addition, the intermediate represented by formula (3a) was 0.45% (=intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100) using column 2 (InertCap WAX). In addition, the amount of byproduct represented by formula (4b) is 1.27% (=byproduct represented by formula (4b) / (all components other than 2-octanol and acetone) × 100).

[0137] Since the solvent used in this embodiment is not used, the hydrogenation yield is low. In addition, it contains a large amount of byproducts represented by formula (4b), resulting in low product purity.

[0138]

[0139] <Comparative Example 2>

[0140] The hydrogenation reaction was carried out in the same manner as in Example 1, except that 2-ethylhexanol was used instead of 2-octanol as the solvent for the hydrogenation reaction. After 15 hours, the amount of the intermediate represented by formula (3a) was 0.30% (= intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100). In addition, the amount of the byproduct represented by formula (4c) was 3.93% (= byproduct represented by formula (4c) / (all components other than 2-octanol and acetone) × 100).

[0141] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 45.81 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%) and diethanol yield 93.14% (=target compound / starting compound×100%)).

[0142] Furthermore, the reaction solution was purified by single distillation using a 300 mL three-necked flask equipped with a thermometer, an N2 bubbling nozzle, and a stir bar (it should be noted that the distillation stage was 1, the distillation temperature was 170–180 °C, and the vacuum degree was 2 torr). After purification, gas chromatography analysis was performed using column 1 (InertCap 1), and the results confirmed that the main fraction containing the target compound represented by formula (1a) was 40.85 g, the diethanol purity was 98.46% (=target compound represented by formula (1a) / (all components other than acetone) × 100)), and the distillation yield was 87.80% (=target compound obtained / target compound input × 100%). In addition, the intermediate represented by formula (3a) was 0.29% (=intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100) using column 2 (InertCap WAX). In addition, the amount of byproduct represented by formula (4c) is 1.26% (=byproduct represented by formula (4c) / (all components other than 2-octanol and acetone) × 100).

[0143] Since the solvent used in this embodiment is not used, the hydrogenation yield is low, and it also contains a large amount of byproducts represented by formula (4c), resulting in low product purity.

[0144]

[0145] <Example 2>

[0146] The hydrogenation reaction was carried out in the same manner as in Example 1, except that tetrahydrolinalool was used instead of 2-octanol as the solvent for the hydrogenation reaction. After 15 hours, the amount of the intermediate represented by formula (3a) was 0.35% (= intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100). In addition, the amount of the byproduct represented by formula (4d) was 0% (= byproduct represented by formula (4d) / (all components other than 2-octanol and acetone) × 100).

[0147] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 48.11 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%) and diethanol yield 97.82% (=target compound / starting compound×100%).

[0148] Furthermore, the reaction solution was purified by single distillation using a 300 mL three-necked flask equipped with a thermometer, an N2 bubbling nozzle, and a stir bar (note that the distillation stage was 1, the distillation temperature was 170–180 °C, and the vacuum degree was 2 torr). After purification, gas chromatography analysis was performed using column 1 (InertCap 1), and the results confirmed that the main fraction containing the target compound represented by formula (1a) was 44.99 g, the diethanol purity was 99.67% (= target compound represented by formula (1a) / (all components other than acetone) × 100)), and the distillation yield was 93.20% (= target compound obtained / target compound input × 100%). In addition, the amount of intermediate represented by formula (3a) was 0.33% (= intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100) using column 2 (InertCap WAX). In addition, the amount of byproduct represented by formula (4d) is 0.00% (=byproduct represented by formula (4d) / (all components other than 2-octanol and acetone) × 100).

[0149] Because the solvent used in this embodiment is used, the hydrogenation yield is high, and there are few byproducts represented by formula (4d), resulting in high product purity.

[0150]

[0151] <Comparative Example 3>

[0152] The hydrogenation reaction was carried out in the same manner as in Example 1, except that cyclohexanol was used instead of 2-octanol as the solvent for the hydrogenation reaction. After 15 hours, the amount of the intermediate represented by formula (3a) was 0.50% (= intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100). In addition, the amount of the byproduct represented by formula (4e) was 0.96% (= byproduct represented by formula (4e) / (all components other than 2-octanol and acetone) × 100).

[0153] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 47.17 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%) and diethanol yield 95.91% (=target compound / starting compound×100%).

[0154] Furthermore, the reaction solution was purified by single distillation using a 300 mL three-necked flask equipped with a thermometer, an N2 bubbling nozzle, and a stir bar (it should be noted that the distillation stage was 1, the distillation temperature was 170–180 °C, and the vacuum degree was 2 torr). After purification, gas chromatography analysis was performed using column 1 (InertCap 1), and the results confirmed that the main fraction containing the target compound represented by formula (1a) was 43.76 g, the diethanol purity was 98.64% (=target compound represented by formula (1a) / (all components other than acetone) × 100)), and the distillation yield was 91.50% (=target compound obtained / target compound input × 100%). In addition, the intermediate represented by formula (3a) was 0.45% (=intermediate represented by formula (3a) / (all components other than 2-octanol and acetone) × 100) using column 2 (InertCap WAX). In addition, the amount of byproduct represented by formula (4e) is 0.91% (=byproduct represented by formula (4e) / (all components other than 2-octanol and acetone) × 100).

[0155] Since the solvent used in this embodiment is not used, the hydrogenation yield is low, and it also contains a large amount of byproducts represented by formula (4e), resulting in low product purity.

[0156]

[0157] The results of the reaction conditions and reaction performance of Examples 1-2 and Comparative Examples 1-3 are shown in Table 1.

[0158] [Table 1]

[0159]

[0160] <Example 3>

[0161] (Obtaining aldehydes)

[0162] The hydroformylation of the monoolefin represented by formula (5a) was carried out in a 500 mL stainless steel reactor. 100 g of the distilled and purified monoolefin represented by formula (5a), 96 g of 2-octanol (manufactured by Kokura Synthetic Industries), 213 mg of triphenyl phosphite (manufactured by Wako Pure Chemical Industries) (1500 mol ppm relative to the monoolefin), and 355 μg of Rh(acac)(CO)2 (manufactured by NEChemcat) (3 mol ppm relative to the monoolefin) were added to the reactor. After purging the reactor atmosphere three times with nitrogen and CO / H2 mixed gases, the system was pressurized with CO / H2 mixed gas, and the reaction was carried out at 100 °C and 2 MPa for 3 hours.

[0163] After the reaction was completed, the reaction solution was analyzed by gas chromatography and GC-MS. The results showed that the reaction solution containing 112.6 g of the starting compound represented by the above formula (2a) was obtained as the main product (substrate conversion rate 100% (=(introduced monoolefin - residual introduced monoolefin) / introduced monoolefin)×100%), and the aldehyde yield was 99.5% (=main product / introduced monoolefin×100%).

[0164] Next, the starting compound represented by formula (2a) is purified by distillation, and a portion of it is supplied to the subsequent reaction.

[0165] (Reduction by a catalyst)

[0166] In a 300 mL stainless steel reactor equipped with a nitrogen bubbling nozzle, 54.94 g of the distilled and purified raw material compound represented by formula (2a), 8.24 g of Cu-Zn-Al catalyst (manufactured by Nichibukai Chemical Co., Ltd.: E-01X), and 120.86 g of tetrahydrolinalool (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. After the atmosphere inside the reactor was replaced three times with nitrogen and H2 gas respectively, the system was pressurized with H2 gas, and the catalyst was reduced at 150°C and 2 MPa for 1 hour. A trap was installed on the exhaust line, and while maintaining 150°C, the pressure was reduced to 0 MPa. Nitrogen gas was then flowed in small amounts through the nitrogen bubbling nozzle to remove the reduced water in the reaction solution. The trap volume was 6.29 g.

[0167] (Dimethyl alcohol is obtained through hydrogenation)

[0168] Next, after three cycles of atmosphere replacement within the reactor using H2 gas, the system was pressurized with H2 gas, and the hydrogenation reaction was carried out at 215°C and 8.0 MPa. Specifically, tetrahydrolinalool was used as the solvent for the hydrogenation reaction. Samples were taken every 5 or 10 hours during the reaction.

[0169] The sample solution was diluted with acetone, filtered through a 0.2 μm membrane filter, and then analyzed by gas chromatography and GC-MS. In addition to the target compound represented by formula (1a) as the main product, the ester compound (intermediate) represented by formula (3a) and the transesterification compound (byproduct) with a molecular weight of 378 represented by formula (4d) were also quantitatively analyzed. It should be noted that the quantitative analysis was performed using analytical column 2 (InertCapWAX). After 50 hours, the amount of the intermediate represented by formula (3a) was 0.50% (=intermediate represented by formula (3a) / (all components other than tetrahydrolinalool and acetone) × 100). Furthermore, the amount of the byproduct represented by formula (4d) was 0.00% (=byproduct represented by formula (4d) / (all components other than tetrahydrolinalool and acetone) × 100).

[0170] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 47.96 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%)) and the yield of the target compound was 97.50% (=target compound / starting compound×100%)).

[0171] Furthermore, the reaction solution was purified by single distillation using a 300 mL three-necked flask equipped with a thermometer, a nitrogen bubbling nozzle, and a stir bar (1 distillation stage, distillation temperature 170–180 °C, vacuum 2 torr). After purification, gas chromatography analysis was performed using column 1 (InertCap 1), confirming the presence of 45.05 g of the main fraction of the target compound represented by formula (1a), a diethanol purity of 99.53% (=target compound represented by formula (1a) / (all components other than acetone) × 100)), and a distillation yield of 93.50% (=target compound obtained / target compound input × 100%). In addition, analysis was performed using column 2 (InertCap WAX), and the amount of the intermediate represented by formula (3a) was 0.48% (=intermediate represented by formula (3a) / (all components other than acetone) × 100). In addition, the amount of byproduct represented by formula (4d) is 0.00% (=byproduct represented by formula (4d) / (all components other than acetone) × 100).

[0172] <Example 4>

[0173] The amount of catalyst in the reduction was adjusted to 5.22 g, and the hydrogenation reaction temperature was set to 225 °C. Otherwise, the hydrogenation reaction was carried out in the same manner as in Example 3. After 20 hours, the amount of the intermediate represented by formula (3a) was 0.66% (= intermediate represented by formula (3a) / (all components other than tetrahydrolinalool and acetone) × 100). In addition, the amount of the byproduct represented by formula (4d) was 0% (= byproduct represented by formula (4d) / (all components other than tetrahydrolinalool and acetone) × 100).

[0174] After the reaction was completed, the reaction solution was analyzed by gas chromatography using column 1 (InertCap1) to confirm that the reaction solution contained 47.88 g of the target compound represented by formula (1a) (substrate conversion 100% (=(starting compound - residual starting compound) / starting compound)×100%) and diethanol yield 97.34% (=target compound / starting compound×100%).

[0175] Furthermore, the reaction solution was purified by single distillation using a 300 ml three-necked flask equipped with a thermometer, an N2 bubbling nozzle, and a stirrer (1 distillation stage, distillation temperature 170–180 °C, vacuum 2 torr). After purification, gas chromatography analysis was performed using column 1 (InertCap 1), confirming the presence of 43.64 g of the main fraction representing the target compound (1a), a diethanol purity of 99.51% (=target compound (1a) / (all components except acetone) × 100)), and a distillation yield of 90.70% (=target compound obtained / target compound input × 100%). Additionally, analysis was performed using column 2 (InertCap WAX), and the amount of the intermediate (3a) was 0.50% (=intermediate (3a) / (all components except acetone) × 100). In addition, the amount of byproduct represented by formula (4d) is 0.00% (=byproduct represented by formula (4d) / (all components other than acetone) × 100).

[0176] The increased hydrogenation temperature accelerated the reaction rate, improving productivity. Furthermore, no byproducts represented by formula (4d) were identified, resulting in high product purity.

[0177] The reaction conditions and reaction results of Examples 3 to 4 are shown in Table 2.

[0178] [Table 2]

[0179]

[0180] This application is based on Japanese Patent Application No. 2021-067275, filed on April 12, 2021, the contents of which are incorporated herein by reference.

[0181] Industrial availability

[0182] According to the manufacturing method of the present invention, diethanol compounds with a norbornene skeleton that are useful as coating additives, adhesives, resin raw materials, etc., can be manufactured in an industrially advantageous manner.

Claims

1. A method for manufacturing a target compound represented by the following formula (1), wherein, The manufacturing method includes a step (A) in which a mixture containing a raw material compound represented by the following formula (2) and a solvent is supplied to a hydrogenation reduction process in the presence of a catalyst with hydrogenation capability. The solvent is a straight-chain or branched secondary or tertiary alcohol, wherein the secondary alcohol is selected from one or more of 2-octanol, 2-nonanol, 2-decanol, 4-decanol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 2-dodecanool, 2-tridecanol, and 2-tetradecanool; and the tertiary alcohol is selected from one or more of tetrahydrolinalool, 3-methyl-3-heptanol, 3-ethyl-3-pentanol, 4-methyl-4-heptanol, 3,4-dimethyl-3-hexanol, 3,5-dimethyl-3-hexanol, and 3-ethyl-2-methyl-3-pentanol. In formula (1), R represents H, CH3, or C2H5. In the formula (2), R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7 or C4H9.

2. The manufacturing method according to claim 1, wherein, The solvent has a boiling point of 100–230°C.

3. The manufacturing method according to claim 1 or 2, wherein, The content of the intermediate represented by the following formula (3) in the target compound is less than 0.5% by mass. In the formula, R represents H, CH3 or C2H5, and R1 represents CH3, C2H5, C3H7 or C4H9.

4. The manufacturing method according to claim 1 or 2, wherein, The content of the byproduct represented by the following formula (4) in the target compound is less than 0.5% by mass. In the formula, R represents H, CH3, or C2H5, and R2 represents C4H9 or C5H. 11 C6H 13 C7H 15 C8H 17 C9H 19 C 10 H 21 C 11 H 23 C 12 H 25 C 13 H 27 C 14 H 29 .

5. The manufacturing method according to claim 1 or 2, wherein, The solvent is 2-octanol and / or tetrahydrolinalool.

6. The manufacturing method according to claim 1 or 2, wherein, In step (A), the catalyst is activated at a first temperature and a first pressure, and after activation, the feedstock compound is hydrogenated at a second temperature and a second pressure.

7. The manufacturing method according to claim 6, wherein, The second pressure exceeds 5 MPa and is below 20 MPa.

8. The manufacturing method according to claim 6, wherein, The second pressure exceeds 5 MPa and is below 8 MPa.

9. The manufacturing method according to claim 8, wherein, The solvent is a straight-chain or branched tertiary alcohol.

10. The manufacturing method according to claim 9, wherein, The solvent is tetrahydrolinalool.

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