Compound and method for producing the same

Abstract

A method for producing a methyl addition compound, comprising: methylating a dinitrile compound represented by the following formula (1) in the presence of potassium carbonate and dimethyl carbonate to obtain a methyl addition compound represented by the following formula (2), wherein R 1 ~R 4 are each independently hydrogen or methyl, R 1 ~R 4 1 to 3 of them are methyl groups.

Description

Technical Field

[0001] The present invention relates to compounds and methods for their preparation. Background Art

[0002] Compounds obtained by methylating the benzyl position of p-phenylenediethylamine are useful as raw materials for resins such as polyamide. As a method for producing the aforementioned methyl addition compound, a method of methylating phenylacetonitrile and then hydrogenating it is known. For example, Patent Document 1 discloses the use of methyl iodide as a methylating agent and a borane complex as a reducing agent. In addition, Non-Patent Document 1 also discloses the use of methyl iodide as a methylating agent. Non-Patent Document 2 discloses the use of dimethyl carbonate as a methylating agent when phenylacetonitrile is used as a substrate.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application No. 2004-503527

[0006] Non-patent literature

[0007] Non-patent document 1: Tetrahedron, Vol. 32, pp. 487-491 (1976)

[0008] Non-patent document 2: Organic Syntheses, Coll. Vol. 10, p. 640 (2004), Vol. 76, p. 169 (1999) Summary of the invention

[0009] Problem that the invention aims to solve

[0010] In patent document 1 and non-patent document 1, methyl iodide is used as a methylating agent, but methyl iodide is toxic to the human body. In addition, when methyl iodide is used, it is easy to introduce excessive methyl groups, making it difficult to control the number of methyl groups (that is, selective methylation). Therefore, it is necessary to react under low temperature and short time conditions, which is not suitable in industry.

[0011] In Patent Document 1, a borane complex is used as a reduction catalyst. However, the borane complex is expensive and difficult to recycle, and is therefore not industrially suitable.

[0012] An object of the present invention is to provide a method for selectively methylating phthalonitrile compared with the case of using methyl iodide as a methylating agent.

[0013] Solutions for solving problems

[0014] As a result of intensive studies, the present inventors have found that phthalocyanine can be selectively methylated by using potassium carbonate and dimethyl carbonate in combination, and that this is an industrial production method, thereby completing the present invention.

[0015] The present invention includes the following embodiments.

[0016] [1] A method for producing a methyl addition compound, comprising: methylating a dinitrile compound represented by the following formula (1) in the presence of potassium carbonate and dimethyl carbonate to obtain a methyl addition compound represented by the following formula (2);

[0017]

[0018] In formula (2), R 1 ~R 4 are each independently hydrogen or methyl,

[0019] R 1 ~R 4 1 to 3 of them are methyl groups.

[0020] [1-1] The production method according to [1], wherein R 1 ~R 4 2 of them are methyl groups.

[0021] [1-2] The production method according to [1] or [1-1], wherein R 1 and R 2 Any one of them and R 3 and R 4 Any one of them is methyl.

[0022] [2] The production method according to any one of [1] to [1-2], wherein the formula (1) is the following formula (1A), the formula (2) is the following formula (2A),

[0023]

[0024] In formula (2A), R 1 ~R 4 As mentioned above.

[0025] [3] The production method according to any one of [1] to [2], wherein the molar ratio of the potassium carbonate to the dinitrile compound is 2.0 to 3.5.

[0026] [3-1] The production method according to any one of [1] to [3], wherein the molar ratio of the potassium carbonate to the dinitrile compound is 2.0 to 3.0.

[0027] [3-2] The production method according to any one of [1] to [3-1], wherein the molar ratio of the potassium carbonate to the dinitrile compound is 2.0 to 2.5.

[0028] [3-1A] The production method according to any one of [1] to [3-2], wherein the molar ratio of the dimethyl carbonate to the dinitrile compound is 3.0 to 18.0.

[0029] [3-2A] The production method according to any one of [1] to [3-1A], wherein the molar ratio of the dimethyl carbonate to the dinitrile compound is 5.0 to 14.0.

[0030] [3-3A] The production method according to any one of [1] to [3-2A], wherein the molar ratio of the dimethyl carbonate to the dinitrile compound is 7.0 to 10.0.

[0031] [4] The production method according to any one of [1] to [3-3A], wherein the methylation is carried out at 180 to 230°C.

[0032] [4-1] The production method according to any one of [1] to [4], wherein the methylation is carried out at 190 to 220°C.

[0033] [4-2] The production method according to any one of [1] to [4-1], wherein the methylation is performed at 200 to 210°C.

[0034] [5] A method for producing a diamino compound, comprising: hydrogenating a methyl addition compound produced by the production method described in any one of [1] to [4-2] to obtain a diamino compound represented by the following formula (3),

[0035]

[0036] In formula (3), R 1 ~R 4 As mentioned above.

[0037] [6] The production method according to [5], wherein the above formula (3) is the following formula (3A),

[0038]

[0039] In formula (3A), R 1 ~R 4 As mentioned above.

[0040] [7] The production method according to [5] or [6], wherein the hydrogenation is carried out in the presence of a solid hydrogenation catalyst.

[0041] [7-1] The production method according to any one of [5] to [7], wherein the hydrogenation is performed in the presence of a Raney catalyst.

[0042] [7-2] The production method according to any one of [5] to [7-1], wherein the hydrogenation is performed in the presence of Raney cobalt.

[0043] [8] a compound selected from the group consisting of diamino compounds represented by the following formulae (3-1) to (3-7),

[0044]

[0045] [9] A compound selected from the group consisting of methyl addition compounds represented by the following formulas (2-1) and (2-2),

[0046]

[0047] Effects of the Invention

[0048] According to the present invention, a method for selectively methylating phthalonitrile can be provided. DETAILED DESCRIPTION

[0049] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto and various modifications can be made without departing from the gist of the present invention.

[0050] <Method for producing compound>

[0051] (Methylation reaction)

[0052] One embodiment of the present invention relates to a method for producing a methyl addition compound, comprising: methylating a dinitrile compound represented by the following formula (1) in the presence of potassium carbonate and dimethyl carbonate to obtain a methyl addition compound represented by the following formula (2).

[0053]

[0054]

[0055] [Where R 1 ~R 4 are each independently hydrogen or methyl,

[0056] R 1 ~R 4 1 to 3 of them are methyl groups.]

[0057] In the production method of the present embodiment, potassium carbonate and dimethyl carbonate are used in combination, so that the dinitrile compound represented by formula (1) can be selectively methylated. In the present specification, "selectively methylate" means controlling the number of methyl groups introduced.

[0058] R 1 ~R 4 1 to 3 of which are methyl groups, preferably R 1 ~R 4 2 of which are methyl groups, and more preferably R 1 and R 2 Any one of them and R 3 and R 4 Any one of them is methyl.

[0059] Although not particularly limited, Formula (1) and Formula (2) are preferably the following Formula (1A) and Formula (2A), respectively.

[0060]

[0061] [Where R 1 ~R 4 As mentioned above]

[0062] The molar ratio of potassium carbonate to the dinitrile compound is preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and even more preferably 2.0 to 2.5. By being within the above range, R 1 and R 2 Any one of them and R 3 and R 4 A compound wherein any one of the above is a methyl group.

[0063] The molar ratio of dimethyl carbonate to the dinitrile compound is preferably 3.0 to 18.0, more preferably 5.0 to 14.0, and still more preferably 7.0 to 10.0. When the molar ratio is 3.0 or more, the reaction becomes faster, and when the molar ratio is 18.0 or less, the economic efficiency can be improved.

[0064] The reaction temperature of the methylation reaction is preferably 180 to 230° C., more preferably 190 to 220° C., and further preferably 200 to 210° C. By keeping the temperature within the above range, R 1 and R 2 Any one of them and R 3 and R 4 A compound wherein any one of the above is a methyl group.

[0065] The methylation reaction may be carried out until the reaction is completed, and examples of the reaction time include 2 to 16 hours, 4 to 12 hours, or 6 to 8 hours.

[0066] (Hydrogenation reaction)

[0067] The production method of the present embodiment may further include a step of hydrogenating the methyl addition compound obtained by the above-mentioned methylation reaction to obtain a diamino compound represented by the following formula (3).

[0068]

[0069] [Where R 1 ~R 4 As mentioned above]

[0070] Although not particularly limited, Formula (3) is preferably the following Formula (3A).

[0071]

[0072] [Where R 1 ~R 4 As mentioned above]

[0073] Hydrogenation is preferably implemented in the presence of a hydrogenation catalyst and in a hydrogen atmosphere. As a hydrogenation catalyst, the catalyst used in the common nitrile hydrogenation reaction can also be adopted, specifically, a catalyst containing Ni and / or Co can be used. Usually, Ni and / or Co are suitably used to be loaded on Al2O3, SiO2, diatomaceous earth, SiO2-Al2O3, and ZrO2 using a precipitation method to form a Raney catalyst such as a Raney catalyst, Raney nickel or Raney cobalt. Solid catalysts are suitable in industrial manufacture because they can be used repeatedly. Among them, from the viewpoint of more effectively and effectively reacting, Raney cobalt catalysts and Raney nickel catalysts are preferably used. Catalysts are used alone or in combination of more than two kinds.

[0074] The mass ratio of the methyl addition compound to the hydrogenation catalyst is preferably 2 to 30, more preferably 5 to 20, and still more preferably 8 to 10. When the mass ratio of the methyl addition compound to the hydrogenation catalyst is within the above range, the yield and selectivity of the obtained diamine compound tend to be improved.

[0075] The hydrogenation reaction may also adopt a solvent commonly used in hydrogenation reactions, specifically, alcohols such as liquid ammonia, aqueous ammonia, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol, and aromatic hydrocarbons such as meta-xylene, mesitylene, and pseudocumene. The solvent may be used alone or in combination of two or more.

[0076] The molar ratio of ammonia to the methyl addition compound is preferably 10 to 150, more preferably 25 to 100, and still more preferably 40 to 50. When the molar ratio is 10 or more, there is a tendency that high boiling compounds such as dimers are reduced and the product is improved, and when the molar ratio is 150 or less, the time taken for the subsequent removal of liquid ammonia is shortened, and the production efficiency is improved.

[0077] The reaction temperature of the hydrogenation reaction is preferably 40 to 160° C., more preferably 60 to 140° C., and further preferably 80 to 120° C. When the reaction temperature of the hydrogenation reaction is 40° C. or higher, the reactivity is improved, and when the reaction temperature of the hydrogenation reaction is 160° C. or lower, there is a tendency for high boiling compounds such as dimers to decrease.

[0078] The pressure of the hydrogenation reaction is preferably 1 to 20 MPa, more preferably 4 to 16 MPa, and still more preferably 8 to 12 MPa. When the pressure of the hydrogenation reaction is within the above range, the yield and selectivity of the obtained diamine compound tend to be improved.

[0079] The hydrogenation reaction may be carried out until the reaction is completed, and examples of the reaction time include 0.5 to 8 hours, 1 to 6 hours, or 2 to 4 hours.

[0080] <Compound>

[0081] One embodiment of the present invention relates to diamino compounds represented by the following formulae (3-1) to (3-7).

[0082]

[0083] The present invention relates to methyl addition compounds represented by the following formulas (2-1) and (2-2).

[0084]

[0085] Example

[0086] The present invention will be described in more detail below using examples, but the technical scope of the present invention is not limited thereto.

[0087] [Example 1]

[0088] (1. Methylation)

[0089] 25.2 g of 1,4-phenyldiacetonitrile, 125 g of dimethyl carbonate, and 50.5 g of potassium carbonate as a base were placed in a 300 mL SUS316 pressure-resistant container, and after nitrogen substitution, the container was heated to 210° C. to perform a methylation reaction for 6.8 hours.

[0090] After the reaction was completed, the mixture was cooled to room temperature naturally to release the generated carbon dioxide. 200 mL of water and 200 mL of diethyl ether solvent were added for liquid separation, the organic solvent layer was recovered, and the solvent was distilled off using a rotary evaporator. The obtained crystals were analyzed by gas chromatography. As a result, the reaction yield of 2,2'-(1,4-phenylene)dipropionitrile as a 2-methyl adduct (2-methylated body) was 90.3%.

[0091] The details of gas chromatography mentioned in the examples are as follows: It should be noted that the reaction yields were all calculated from the area percentage of the components detected by gas chromatography.

[0092] Model name: GC2010PLUS, manufactured by Shimadzu Corporation

[0093] Chromatographic column: Product name "HP-1ms", manufactured by Agilent Technologies, length 30m x inner diameter 0.25mm, film thickness 0.25μm

[0094] Conditions: Carrier gas, He (constant pressure: 73.9 kPa)

[0095] Inlet temperature: 300℃

[0096] Detector: FID

[0097] Detector temperature: 300°C

[0098] Column oven temperature: Start at 50°C, increase to 175°C at 5°C / min, increase to 320°C at 20°C / min, and maintain at 320°C for 30 minutes

[0099] (2. Hydrogenation)

[0100] After 29.0 g of 2,2'-(1,4-phenylene)dipropionitrile synthesized as described above, 105 g of liquid ammonia as a solvent, and 2.99 g of Raney cobalt (manufactured by Gules) as a catalyst were placed in a 300 mL SUS316 pressure-resistant container, hydrogen was introduced into the container until the reaction pressure reached 4 MPa. Then, the container was heated to a reaction temperature of 100°C. After reaching the specified temperature, hydrogen was continuously supplied to the container in a manner that hydrogen gas was constantly maintained at a reaction pressure of 10 MPa, while the container was stirred at 750 rpm by an electromagnetic stirring blade, and an amination reaction (nitrile hydrogenation reaction) by hydrogenation was carried out for 180 minutes. After the reaction was completed, the liquid ammonia was distilled off, and the reaction product was dissolved in methanol, the catalyst was removed, and then analyzed by gas chromatography. As a result, the reaction yield of 2,2'-(1,4-phenylene)bis(propane-1-amine) as a dimethyl adduct (dimethylated form) was 92.5%, the reaction yield of the monoadduct was 0.5%, and the reaction yield of the triadduct was 0.7%.

[0101] [Example 2]

[0102] 5.0 g of 1,4-benzenediacetonitrile, 56.1 g of dimethyl carbonate, and 18.9 g of potassium carbonate as a base were placed in a 300 mL SUS316 pressure-resistant container, the atmosphere was replaced with nitrogen, and the container was heated to 205° C. to perform a methylation reaction for 6.7 hours.

[0103] After the reaction was completed, the mixture was cooled to room temperature naturally to release the generated carbon dioxide. 200 mL of water and 200 mL of diethyl ether solvent were added for liquid separation, the organic solvent layer was recovered, and the solvent was distilled off using a rotary evaporator. The obtained crystals were analyzed by gas chromatography. As a result, the reaction yield of 2,2'-(1,4-phenylene)dipropionitrile as a 2-methyl adduct (2-methylated body) was 70.0%.

[0104] [Example 3]

[0105] 5.0 g of 1,4-phenyldiacetonitrile, 55.3 g of dimethyl carbonate, and 18.8 g of potassium carbonate as a base were placed in a 300 mL SUS316 pressure-resistant container, the atmosphere was replaced with nitrogen, and the container was heated to 170° C. to perform a methylation reaction for 6.7 hours.

[0106] After the reaction was completed, the mixture was cooled to room temperature naturally to release the generated carbon dioxide. 200 mL of water and 200 mL of diethyl ether solvent were added for liquid separation, the organic solvent layer was recovered, and the solvent was distilled off using a rotary evaporator. The obtained crystals were analyzed by gas chromatography. As a result, the reaction yield of 2,2'-(1,4-phenylene)dipropionitrile as a 2-methyl adduct (2-methylated body) was 30.7%.

[0107] [Example 4]

[0108] 5.0 g of 1,4-phenyldiacetonitrile, 54.8 g of dimethyl carbonate, and 18.7 g of potassium carbonate as a base were placed in a 300 mL SUS316 pressure-resistant container, the atmosphere was replaced with nitrogen, and the container was heated to 245° C. to perform a methylation reaction for 6.7 hours.

[0109] After the reaction was completed, the mixture was cooled to room temperature naturally to release the generated carbon dioxide. 200 mL of water and 200 mL of diethyl ether solvent were added for liquid separation, the organic solvent layer was recovered, and the solvent was distilled off using a rotary evaporator. The obtained crystals were analyzed by gas chromatography. As a result, the reaction yield of 2,2'-(1,4-phenylene)dipropionitrile as a 2-methyl adduct (2-methylated body) was 1.3%.

[0110] The results of Examples 1 to 4 are shown in Table 1.

[0111] [Table 1]

[0112] Table 1

[0113]

[0114] This application claims priority based on Japanese Patent Application No. 2021-073893 (filed on April 26, 2021), the entire contents of which are incorporated herein by reference.

Claims

1. A method for producing a methyl addition compound, comprising: A step of methylating a dinitrile compound represented by the following formula (1) in the presence of potassium carbonate and dimethyl carbonate to obtain a methyl addition compound represented by the following formula (2), wherein the molar ratio of the potassium carbonate to the dinitrile compound is 2.0 to 3.5, the molar ratio of the dimethyl carbonate to the dinitrile compound is 7.0 to 10.0, and the methylation is carried out at 190 to 230° C., In formula (2), R 1 ~R 4 are each independently hydrogen or methyl, R 1 ~R 4 2 of which are methyl groups, and R 1 and R 2 Any one of them and R 3 and R 4 Any one of them is methyl.

2. The manufacturing method according to claim 1, wherein: The formula (1) is the following formula (1A), and the formula (2) is the following formula (2A), In formula (2A), R 1 ~R 4 As described in claim 1.

3. The manufacturing method according to claim 1 or 2, wherein: The molar ratio of the potassium carbonate to the dinitrile compound is 2.0 to 2.

5.

4. A method for producing a diamino compound, comprising: A step of producing a methyl addition compound by the production method according to any one of claims 1 to 3, and hydrogenating the methyl addition compound to obtain a diamino compound represented by the following formula (3), In formula (3), R 1 ~R 4 As described in claim 1.

5. The manufacturing method according to claim 4, wherein: The formula (3) is the following formula (3A), In formula (3A), R 1 ~R 4 As described in claim 1.

6. The manufacturing method according to claim 4 or 5, wherein: The hydrogenation is carried out in the presence of a solid hydrogenation catalyst.

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