Method for producing dimethyl perhydro-1, 4: 5, 8-dimethylnaphthalene-2, 3-dicarboxylate

Abstract

Provided is a method for producing a compound represented by formula (1), the method comprising a step for crystallizing the compound represented by formula (1) from a crystallization solution, the crystallization solution contains: a compound represented by formula (1); 0.5-7 parts by weight of at least one compound selected from the group consisting of aliphatic hydrocarbons having 5-10 carbon atoms and aromatic hydrocarbons having 6-9 carbon atoms per 1 part by weight of the compound represented by formula (1); and 0.3-6% by weight of a compound represented by formula (2) relative to the compound represented by formula (1). # imgabs0 # imgabs1 #

Description

Technical Field

[0001] The present invention relates to a method for producing dimethyl perhydro-1,4:5,8-dimethylnaphthalene-2,3-dicarboxylate and a crystalline composition obtained by the production method. Background Art

[0002] Perhydro-1,4:5,8-dimethylnaphthalene-2,3-dicarboxylic acid derivatives such as dimethyl perhydro-1,4:5,8-dimethylnaphthalene-2,3-dicarboxylate represented by the following formula (1) are known as raw materials for polyester resins having excellent heat resistance, transparency, and dimensional stability (e.g., Non-Patent Document 1).

[0003] [Chemistry 1]

[0004]

[0005] In addition, as a method for industrially producing the compound represented by the above-mentioned formula (1) (it should be noted that hereinafter, the "compound represented by the (general) formula (○)" may be referred to as the "compound of formula (○)" (○ represents the formula number).), for example, the method described in Patent Document 1 is known. According to this production method, the compound of formula (1) can be produced with relatively high purity while suppressing the generation of impurities derived from the by-produced dicyclopentadiene polymer.

[0006] Prior art literature

[0007] Non-patent literature

[0008] Non-patent literature 1: Journal of Polymer Science: Polymer Chemistry Edition, vol. 10, 3191-3204 (1972)

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-161067 Summary of the Invention

[0011] Problems to be solved by the invention

[0012] By combining the production method described in the above-mentioned patent document with distillation, rectification, etc. used as needed, the content of high molecular weight components in the impurities derived from the aforementioned dicyclopentadiene polymer can be reduced. However, low molecular weight impurities, specifically the compound represented by the following general formula (4), have a boiling point close to that of the compound of formula (1), and are difficult to remove to a degree exceeding that described in the above-mentioned patent document even by repeated distillation, purification, etc.

[0013] [Chemistry 2]

[0014]

[0015] (In the formula, n represents 1 or 2.)

[0016] An object of the present invention is to provide a method for producing a compound of formula (1) that can eliminate or further reduce the compound represented by the above-mentioned general formula (4).

[0017] Means for solving problems

[0018] The present inventors have conducted intensive studies to solve the above problems and have found that a method for producing a compound of formula (1) comprising the following steps can solve the above problems. Specifically, the present invention includes the following inventions.

[0019] [1] A method for producing a compound represented by the following formula (1):

[0020] [Chemistry 3]

[0021]

[0022] The production method includes the step of crystallizing the compound represented by the above formula (1) from a crystallization solution.

[0023] The crystallization solution comprises the compound represented by the above formula (1), 0.5 to 7 parts by weight of at least one compound selected from aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 9 carbon atoms, based on 1 part by weight of the compound represented by the above formula (1), and 0.3 to 6% of the compound represented by the following formula (2) based on the compound represented by the above formula (1).

[0024] [Chemistry 4]

[0025]

[0026] [2] A crystalline composition, wherein the content of the compound represented by the following formula (1) is 90% or more,

[0027] [Chemistry 5]

[0028]

[0029] The content of the compound represented by the following formula (3) is 0.2 to 5%,

[0030] [Chemistry 6]

[0031]

[0032] The total content of the compounds represented by the following general formula (4) is 0.2% or less,

[0033] [Chemistry 7]

[0034]

[0035] (Wherein, n represents 1 or 2.).

[0036] [3] The crystalline composition according to [2], wherein the content of the compound represented by the following formula (2) is 3% or less.

[0037] [Chemistry 8]

[0038]

[0039] Effects of the Invention

[0040] According to the present invention, a method for producing a compound of formula (1) in which the residual amount of the compound represented by general formula (4) is significantly reduced can be provided.

[0041] Furthermore, the compound of formula (1) obtained by the production method of the present invention substantially does not contain the compound represented by the above-mentioned general formula (4). Furthermore, it was found that the crystalline composition of the present invention, in which the compound represented by the above-mentioned general formula (4) is significantly reduced and which contains a certain amount of the compound represented by the following formula (3), has excellent blocking resistance.

[0042] [Chemistry 9]

[0043]

[0044] Therefore, according to the present invention, a crystalline composition containing the compound of formula (1) as a main component and having excellent blocking resistance as required can also be provided. DETAILED DESCRIPTION

[0045] In the present invention, when a range is expressed as "A to B", unless otherwise specified, it means A or more and B or less. In addition, the so-called "content" in the present invention, unless otherwise specified, is the area percentage value of the gas chromatogram measured under the conditions described in Example 1 described later. It should be noted that, regarding the content in the crystallization solution, since the correct content may not be calculated using the area percentage value of the gas chromatogram of the solution, the "content relative to the compound of formula (1)" (the value calculated by {(area percentage value of the compound of formula (●)) / [(area percentage value of the compound of formula (●))+(area percentage value of the compound of formula (1))]}×100 using the area percentage value of the gas chromatogram measured under the conditions described in Example 1 described later (● represents a formula number other than 1)) is used as the "content".

[0046] <Method for producing the compound of formula (1) of the present invention>

[0047] The production method of the present invention is characterized by comprising the step of crystallizing the compound of formula (1) from a crystallization solution containing the compound, at least one compound selected from aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 9 carbon atoms, and the compound of formula (2).

[0048] The compound of formula (1) provided in the production method of the present invention can be produced by a known production method. It should be noted that, from the perspective of providing a crystalline composition comprising the compound of formula (1) with excellent blocking resistance, the compound of formula (1) used for crystallization may further contain the compound of formula (3), with the content of the compound of formula (3) being, for example, 1.5 to 6.5% relative to the compound of formula (1).

[0049] The aliphatic hydrocarbon having 5 to 10 carbon atoms used in the present invention may have a branched chain or may have a halogen atom. Specific examples include n-pentane, n-hexane, 1-chlorohexane, 1-bromohexane, 3-methylpentane, 2-methylpentane, 2,3-dimethylbutane, cyclohexane, n-heptane, 1-chloroheptane, 1-bromoheptane, 2-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, n-octane, 2-methylheptane, 2,2-dimethylhexane, 2,2,3-trimethylpentane, 2,2,3,3-tetramethylbutane, n-nonane, 2-methyloctane, 2,2-dimethylheptane, 2,2,3-trimethylhexane, 2,2,3,3-tetramethylpentane, n-decane, 2-methylnonane, 2,2-dimethyloctane, 2,2,3-trimethylheptane, 2,2,3,3-tetramethylhexane, 4-propylheptane, and 3,4-diethylhexane. The aromatic hydrocarbons having 6 to 9 carbon atoms used in the present invention may also have a halogen atom. Specific examples thereof include benzene, chlorobenzene, bromobenzene, toluene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, o-xylene, m-xylene, p-xylene, α-chloro-p-xylene, 4-chloro-o-xylene, α-bromo-p-xylene, 4-bromo-o-xylene, and mesitylene. Among these aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 9 carbon atoms, aliphatic hydrocarbons having 5 to 10 carbon atoms are preferred, and n-hexane, n-heptane, cyclohexane, and n-octane are more preferred. Furthermore, the content of at least one compound selected from aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 9 carbon atoms in the crystallization solution (the total content of these compounds when two or more are present) is 0.5 to 7 parts by weight, preferably 1 to 6 parts by weight, relative to 1 part by weight of the compound of formula (1).

[0050] The compound of formula (2) used in the present invention may be contained in the compound of formula (1) provided in the present invention, or may be synthesized separately and added to the crystallization solution during the practice of the present invention. However, the present invention can be practiced more easily when the compound of formula (2) is contained in the compound of formula (1) provided in the present invention. The compound of formula (1) containing the compound of formula (2) can be produced, for example, by the method of Patent Document 1.

[0051] The compound of formula (2) contained in the crystallization solution should be contained in an amount of 0.3 to 6%, preferably 0.5 to 4.5%, relative to the compound of formula (1). If the content of the compound of formula (2) is less than 0.3%, the compound of formula (4) may not be reduced. If the content of the compound of formula (2) is greater than 6%, the yield of the compound of formula (1) may be reduced.

[0052] The method for crystallizing the compound of formula (1) can be carried out by conventional methods. Specifically, for example, the method can be carried out by adding the compound of formula (1), at least one compound selected from the above-mentioned aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 9 carbon atoms, and the compound of formula (2) to a reactor, then setting the internal temperature to 60 to 80°C to completely dissolve the compound of formula (1), and then cooling the reactor to -5 to 10°C at a rate of 0.05 to 0.3°C / min to precipitate crystals, and filtering the obtained crystals at -5 to 10°C.

[0053] The crystallization step can be repeated as needed. In addition, the obtained crystals can be dried as needed, or can be appropriately subjected to conventional purification operations such as adsorption, steam distillation, and recrystallization.

[0054] <Crystalline Composition of the Present Invention>

[0055] The crystalline composition of the present invention comprises the compound of formula (1) as a main component, the compound of formula (3) as a minor component, and substantially no compound of formula (4). The content of the compound of formula (1) in the crystalline composition of the present invention is generally 90% or more, preferably 94% or more. The upper limit is not particularly limited, but is, for example, 99.5% or less, preferably 99% or less.

[0056] The content of the compound of formula (3) contained in the crystalline composition of the present invention needs to be 0.2 to 5%, and preferably 0.5 to 3.5%.

[0057] The content of the compound of formula (4) contained in the crystalline composition of the present invention needs to be 0.2% or less, and preferably 0.1% or less.

[0058] The content of the compound of formula (2) in the crystalline composition of the present invention is not particularly limited, but is typically 3% or less, preferably 2% or less. By reducing the content of the compound of formula (2), a crystalline composition of higher purity can be provided.

[0059] Such a crystalline composition of the present invention is characterized by excellent blocking resistance.

[0060] Example

[0061] The present invention will be described in detail below with reference to Examples, etc. However, the present invention is not limited in any way by these Examples. It should be noted that the compound of formula (1) used in the following Examples, etc. is a compound produced according to the method described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2021-161067).

[0062] [1] Gas chromatography (GC) analysis

[0063] ·Equipment: Equivalent to Shimadzu Corporation's gas chromatograph GC-2014

[0064] Column: Agilent DB-5HT (film thickness 0.10 μm × inner diameter 0.25 mm × length 30.0 m)

[0065] ·Column temperature: 70℃(1min)→10℃ / min→160℃(2min)→10℃ / min→210℃(2min)→10℃ / min→350℃(2min)

[0066] Vaporization chamber temperature: 300℃

[0067] Detector temperature: 360°C

[0068] Detector: FID

[0069] Carrier gas: N2 (50ml / min)

[0070] Combustion gas: hydrogen (40ml / min), air (400ml / min)

[0071] Injection volume: 1 μL

[0072] Sample preparation method:

[0073] About 100 mg of a sample was weighed in a 10 mL volumetric flask, and the volume was fixed with toluene. The resulting liquid was designated as the sample solution.

[0074] The area percentage values ​​of gas chromatography refer to values ​​obtained by expressing the peak area values ​​of the compounds represented by formulae (1) to (4) as percentages after removing the toluene peak in the chromatogram obtained by GC analysis.

[0075] <Blocking resistance test>

[0076] 80 g of the sample was placed in a zipper-type polyethylene bag, a load of 2.0 kPa was uniformly applied, and the bag was left to stand for 5 days in a 60°C atmosphere. The sample was then removed and visually inspected for the presence of blocking. Blocking resistance was evaluated by rating the sample as "◯" for no blocking and "×" for the presence of blocking.

[0077] <Example 1>

[0078] Into a four-necked flask equipped with a stirring device and a condenser, 250 g of the compound of formula (1) (purity (content of the compound of formula (1), area percentage by gas chromatography): 94.4%, content of the compound of formula (2): 4.0% (content relative to the compound of formula (1): 4.1%), content of the compound of formula (3): 1.1% (content relative to the compound of formula (1): 1.2%), content of the compound of formula (4): 0.5% (content relative to the compound of formula (1): 0.5%)) and 500 g of n-heptane as a solvent (2 parts by weight relative to 1 part by weight of the compound of formula (1)) were added. The contents were heated to 50°C and stirred at the same temperature for 1 hour to completely dissolve the crystals to obtain a crystallization solution. The obtained crystallization solution was cooled at 0.2°C / min, and crystals precipitated when the solution was set to 25°C. Thereafter, the solution was stirred at the same temperature for 1 hour. The mixture was further cooled to 0°C and stirred at the same temperature for 1 hour, then filtered and dried at an internal temperature of 45-50°C for 4 hours under a reduced pressure of 1.9 kPa. This yielded 198 g of a crystalline composition containing the compound of formula (1). The composition (content of each component) of the resulting crystalline composition is shown in Table 1. The results of the anti-blocking test are also shown in Table 2.

[0079] <Examples 2 to 10>

[0080] A crystalline composition was obtained in the same manner as in Example 1, except that the compound of formula (1) used, the type of solvent added, and the amount of solvent added were changed as shown in Table 1. The composition (content of each component) of the obtained crystalline composition is shown in Table 1. In addition, the results of the blocking resistance test are shown in Table 2.

[0081] Comparative Examples 1 to 4

[0082] The same procedure as in Example 1 was followed except that the compound of formula (1) used, the type of solvent added, and the amount of solvent added were changed as shown in Table 1. However, even after cooling to 0°C and stirring at the same temperature for 1 hour, no crystals were precipitated.

[0083] Reference Examples 1 and 2

[0084] The solidified compound of formula (1) was pulverized, and the resulting powder was subjected to a blocking resistance test. The results are shown in Table 2. In Reference Example 1, the compound of formula (1) used in Example 1 was used as the solidified compound of formula (1), and in Reference Example 2, the compound of formula (1) used in Example 6 was used as the solidified compound of formula (1).

[0085]

[0086]

Claims

1. A method for producing a compound represented by the following formula (1): The production method comprises the step of crystallizing the compound represented by formula (1) from a crystallization solution. The crystallization solution comprises the compound represented by the formula (1), 0.5 to 7 parts by weight of at least one compound selected from aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 9 carbon atoms, based on 1 part by weight of the compound represented by the formula (1), and 0.3 to 6% of the compound represented by the following formula (2) based on the compound represented by the formula (1). 。 2. A crystalline composition, wherein The content of the compound represented by the following formula (1) is 90% or more, The content of the compound represented by the following formula (3) is 0.2% to 5%, The total content of the compounds represented by the following general formula (4) is 0.2% or less, In the formula, n represents 1 or 2.

3. The crystalline composition according to claim 2, wherein The content of the compound represented by the following formula (2) is 3% or less, 。

Images