WO2007100047A1

WO2007100047A1 - Method for producing 2-imidazolidinone compound and 4,5-dialkoxy-2-imidazolidinone compound

Info

Publication number: WO2007100047A1
Application number: PCT/JP2007/053923
Authority: WO
Inventors: Shigeyoshi Nishino; Hidetaka Shima
Original assignee: Ube Industries, Ltd.
Priority date: 2006-03-02
Filing date: 2007-03-01
Publication date: 2007-09-07
Also published as: CN101395140B; JPWO2007100047A1; CN101395140A

Abstract

The present invention aims to produce a 2-imidazolidinone compound and a 4,5-dialkoxy-2-imidazolidinone compound by a simple method with high yield. Namely, disclosed is a method for commercially advantageously producing a 2-imidazolidinone compound and a 4,5-dialkoxy-2-imidazolidinone compound. Specifically disclosed is a method for producing a 2-imidazolidinone compound, which is characterized by reacting a 4,5-dialkoxy-2-imidazolidinone compound with hydrogen in the presence of a metal catalyst. Also specifically disclosed is a method for producing a 4,5-dialkoxy-2-imidazolidinone compound, which comprises a step for reacting a dicarbonyl compound, a urea compound and an alcohol in the presence of a solid acid catalyst.

Description

Specification

Method for producing 2 imidazolidinone compound and 4,5 dialkoxy 2 imidazolidinone compound

Technical field

[0001] The present invention relates to a 2_imidazolidinone compound and a method for producing a 4,5-dialkoxy_2_imidazolidinone compound which is a raw material for the synthesis thereof. 2_Imidazolidinone compounds and 4,5 dialkoxy 2 imidazolidinone compounds are useful compounds, for example, as raw materials and synthetic intermediates for pharmaceuticals and agricultural chemicals.

Background art

[0002] Conventionally, as a method for producing a 2_imidazolidinone compound, for example, phosgene and 1,3-dimethylethylenediamine are reacted at a low temperature to produce 1,3-dimethyl_2-imidazolide. Non-Patent Document 1 (for example, see Non-patent Document 1), 2_Imidazolidinone and dimethyl sulfate are reacted to obtain 1,3_dimethyl-2-imidazolidinone (for example, see Non-Patent Document 2), Trif A method of obtaining 1,3_dimethyl-2-imidazolidinone by reacting enil antimony, diphosphorus pentasulfide and carbon dioxide under high pressure (for example, see Non-patent Document 3) is disclosed. However, in either method, it is necessary to use highly toxic or expensive reagents, and the reaction conditions are severe, etc. 2_Industrial production of imidazolidinone compounds There was a problem as a method.

[0003] Conventionally, as a method for producing a 4,5 dialkoxy 2 imidazolidinone compound, for example, an aqueous solution of darioxal, 1,3-dimethylurea, 1-butanol and concentrated sulfuric acid are reacted at room temperature. , 5 Dibutoxy 1,3 A method for producing dimethylimidazolidine-2-one is disclosed (for example, see Patent Document 1). However, this method has a problem that much labor and energy are consumed to remove and discard the used acid catalyst (sulfuric acid) from the reaction solution.

Patent Document 1: International Publication WO90 / 00407 Pamphlet

Non-Patent Document 1: J. Chem. So, 1956, 5041.

Non-patent document 2: Synth.Commun., 18 (5), 487 (1988) Non-Patent Document 3: J. Org. Chem., 57 (28), 7339 (1992)

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to solve the above-mentioned problems and produce 2-imidazolidinone compounds and 4,5 dialkoxy-2-imidazolidinone compounds in a high yield by a simple method.

Another object of the present invention is to provide a process for producing industrially suitable 2 imidazolidinone compounds and 4,5 dialkoxy 2 imidazolidinone compounds.

Means for solving the problem

[0005] A first subject of the present invention is a compound represented by the general formula (1) in the presence of a metal catalyst.

[0007] (where

R ² and R each represent a hydrogen atom or a hydrocarbon group which may be the same or different, and R ³ represents an alkyl group. )

A general formula (2) characterized by reacting 4,5-dialkoxy _ 2 _ imidazolidinone compound represented by formula (2)

[0008]

[0009] In the formula, R ¹ R ² and R are as defined above, and this is solved by a method for producing a 2_imidazolidinone compound.

[0010] The second subject of the present invention is the general formula (3) in the presence of a solid acid catalyst.

[0011]

(In the formula, R represents a hydrogen atom or a hydrocarbon group.)

Dicarbonyl compounds represented by general formula (4)

[0013] 0

^R1 \ N people N (4)

H H

[In the formula, R ¹ and R ² represent the same or different hydrogen atom or hydrocarbon group.]

Urea compounds represented by general formula (5)

[0015]

R ³ 0H ( ⁵ ) [0016] (wherein R ³ represents an alkyl group)

Which is reacted with an alcohol represented by the general formula (1)

(1)

[0018] (where R,

R ² and R ³ are as defined above. )

It is solved by the method for producing 4,5-dialkoxy_2_imidazolidinone compound shown in

The invention's effect

[0019] According to the present invention, an industrially suitable 2-imidazolidin which produces a 2-imidazolidinone compound and a 4,5-dialkoxy-2-imidazolidinone compound in a high yield by a simple method. It is possible to provide a method for producing a non-compound and a 4,5 dialkoxy 2 imidazolidinone compound.

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] [Method for producing 2_imidazolidinone compound from 4,5-dialkoxy_2_imidazolidinone compound by hydrogenation reaction]

The present invention relates to a 4,5-dialkoxy _ 2 _ imidazolidinone compound represented by the general formula (1) The present invention relates to a process for producing 2-imidazolidinone represented by the general formula (2) by reacting with hydrogen in the presence of a metal catalyst.

[0021] The 4,5 dialkoxy 2 imidazolidinone compound used in the hydrogenation reaction of the present invention is represented by the above general formula (1). In the general formula (1),

R¾TO «represents a hydrogen atom or a hydrocarbon group which may be the same or different, and examples of the hydrocarbon group include carbon number such as methinole group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and the like. 1-6 alkyl groups; C3-C6 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups; C7-C12 aralkyls such as benzyl, phenethyl and phenylpropyl Group: aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, biphenylyl group, naphthyl group and the like. These groups include various isomers.

[0022] R ³ is an alkyl group, and examples thereof include an alkyl group having 1 to 6 carbon atoms such as a methylol group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexynole group. These groups include various isomers.

[0023] The metal catalyst used in the hydrogenation reaction of the present invention includes at least one metal atom selected from the group consisting of palladium, platinum, and nickel. Specifically, for example, palladium / carbon, Examples thereof include palladium / barium sulfate, palladium hydroxide / platinum, platinum / carbon, platinum sulfide / carbon, palladium platinum / carbon, platinum oxide, and Raney Nikkenore. In addition, you may use these metal catalysts individually or in mixture of 2 or more types.

[0024] The amount of the metal catalyst used is preferably from 0.0001 to 0.5 monole, more preferably 0.0, based on one monole of 4,5 dialkoxy 2 imidazolidinone compound in terms of metal atoms.

0002 to 0.1 mono.

[0025] The amount of hydrogen used in the hydrogenation reaction of the present invention is preferably from 0.:! To 20 mol, more preferably from 0.1 to 1 mol per mol of 4,5_dialkoxy_2-imidazolidinone compound. 2

~ 10 monoles.

[0026] The hydrogenation reaction of the present invention is carried out in the presence or absence of a solvent. Solvents that can be used are not particularly limited as long as they do not inhibit the reaction, but water; methanol, Alcohols such as ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene glycol and triethylene glycol; ketones such as acetone, methylethanolketone and methylisobutylketone; N, N dimethylformamide, N, N-dimethylacetate Amides, amides such as N-methylpyrrolidone; Ureas such as N, N, -dimethylimidazolidinone; Sulfoxides such as dimethyl sulfoxide; Examples include ethers such as diisopropyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene. Alcohols are preferably used. These organic solvents may be used alone or in combination of two or more.

[0027] The amount of the solvent to be used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 0 to 50 g with respect to 4,5-dialkoxy-1-imidazolidinone compound lg.

[0028] The hydrogenation reaction of the present invention is performed, for example, by a method of mixing a 4,5_dialkoxy_2-imidazolidinone compound, a metal catalyst and a solvent in a hydrogen atmosphere and reacting them with stirring. . The reaction temperature at that time is preferably 0 to 200 ° C., more preferably 10 to 150 ° C., and the reaction pressure is preferably 0.1 to:! OMPa, more preferably 0.:! To IMP a Get out.

[0029] The 2-imidazolidinone compound obtained in the hydrogenation reaction of the present invention is subjected to, for example, neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, column chromatography after completion of the reaction. It can be isolated and purified by general methods such as

[0030] [Method for producing 4,5-dialkoxy 2-imidazolidinone compound from dicarbonyl compound, urea compound and alcohol (raw material synthesis method 1)]

The present invention comprises reacting a dicarboxylic compound represented by the general formula (3), a urea compound represented by the general formula (4) and an alcohol represented by the general formula (5). It is related to the production method (raw material synthesis method 1) of 4,5-dialkoxy_2_imidazolidinone compound represented by

[0031] The dicarbonyl compound used in the raw material synthesis 1 reaction of the present invention is represented by the general formula (3). In the general formula (3), R represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group. An alkyl group having 1 to 6 carbon atoms such as a propyl group or a hexyl group; a cycloalkyl group having 3 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group; a benzyl group or a phenethyl group; Examples thereof include aralkyl groups having 7 to 12 carbon atoms such as a phenylpropyl group; aryl groups having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a biphenylyl group, and a naphthyl group. These groups include various isomers.

[0032] The dicarboxylic compound can be used as a solution dissolved in water or an organic solvent inert to the reaction, and a multimer or the like (condensed between molecules) can also be used. be able to.

[0033] The urea compound used in the reaction of the raw material synthesis 1 of the present invention is represented by the general formula (4). In the general formula (4), R ¹ and R ² represent hydrogen atoms or hydrocarbon groups which may be the same or different. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, butyl group, an alkyl group having 1 to 6 carbon atoms such as pentyl, hexyl, cyclo-propyl, cyclobutyl group, cyclopentyl group, carbon atoms such as a cyclohexyl group ₃

A cycloalkyl group having ˜6; aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, phenylpropyl group, etc .; an aryl having 6 to 20 carbon atoms such as phenyl group, tolyl group, biphenylyl group, naphthyl group, etc. Groups. These groups include various isomers.

[0034] The amount of urea used in the raw material synthesis 1 reaction of the present invention is preferably 0.8 to: L 2 monole, more preferably 0.9 to 9: L 1 mol per 1 mol of the dicarbonyl compound. It is.

[0035] The alcohol used in the raw material synthesis 1 reaction of the present invention is represented by the general formula (5). In the general formula (5), R ³ is an alkyl group. Examples of the alkyl group include 1 to 6 carbon atoms such as a methinole group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Of the alkyl group. These groups include various isomers.

[0036] The amount of the alcohol used in the raw material synthesis 1 reaction of the present invention is preferably from f to 0.5 to 200 monole, more preferably from f to 2.0. 150 monoles.

[0037] The solid acid catalyst used in the raw material synthesis 1 reaction of the present invention is not particularly limited as long as it is a solid acid having a Bronsted acid point. For example, clay minerals such as acid clay; Amberlite ( Product Name), Dowex (Product Name), Diaion (Product Name), Duolite (Product Name), Levacit (Product Name), Sumikaion (Product Name), etc .; Fluorine such as Nafion Sulfonated resin; silica alumina, zeolite, oxidation A force S including inorganic oxides such as vanadium, preferably a sulfonic acid type cation exchange resin is used. These solid acid catalysts may be used alone or in combination of two or more.

[0038] The amount of the solid acid catalyst to be used is preferably 0.001 to 1.0 g and more preferably (preferably 0.02 to 0.9 g) with respect to the dicarboxylic compound lg.

[0039] The raw material synthesis 1 reaction of the present invention may be carried out in the presence of a solvent other than alcohol. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. Water; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Ureas such as 1,3_dimethylimidazolidinone; Jetyl ether, diisopropyl ether, tetrahydrofuran, Ethers such as dioxane; Aromatic hydrocarbons such as benzene, toluene and xylene; Carboxylic acid esters such as ethyl acetate and butyl acetate; Nitriles such as acetonitrile and propionitryl; Sulfoxides such as dimethyl sulfoxide Preferably, nitriles, ureas, carboxylic acid esters, and aromatic hydrocarbons are used. In addition, you may use these solvents individually or in mixture of 2 or more types.

[0040] The amount of the solvent to be used is appropriately adjusted depending on the uniformity of the reaction solution, the stirring ability, etc., but is preferably 0 to 100 g, more preferably 0 to 50 g based on the urea compound lg.

[0041] The synthesis raw material 1 reaction of the present invention is performed by, for example, a method in which a solid acid catalyst, a dicarbonyl compound, a urea compound, and an alcohol are mixed and then reacted with stirring. The reaction temperature at that time is preferably 0 to 300 ° C, more preferably 20 to 200 ° C, and the reaction pressure is not particularly limited.

[0042] The 4,5-dialkoxy_2_imidazolidinone compound obtained in the raw material synthesis 1 reaction of the present invention is, for example, neutralized, extracted, filtered, concentrated, distilled, recrystallized, crystallized after completion of the reaction. It can be isolated and purified by a general method such as analysis or force chromatography.

[0043] [Method of Producing 4,5-Dialkoxy-2-Imidazolidinone Compound by Esterification of 4,5-Dihydroxy-1,2-Imidazolidinone Compound (Raw Material Synthesis Method 2)]

In the present invention, the 4,5-dialkoxy-1-2-imidazolidinone compound represented by the general formula (1) is represented by the general formula (6) in the presence of a solid acid catalyst. [0044]

[Wherein, R, R ¹ and R ² are as defined above.]

4,5-Dihydroxy _ 2 _ imidazolidinone compound represented by the general formula (5)

[0046] _r3qh (5)

(Wherein R ³ has the same meaning as described above.)

It can also be synthesized by reacting with the alcohol shown in (Material synthesis method 2).

The 4,5 dialkoxy 2 imidazolidinone compound in the present invention is represented by the general formula (6), and R, R ¹ and R ² in the general formula (6) are as defined above. 4,5-Dialkoxy-2-imidazolidinone compounds can be synthesized by known methods or similar methods.

[0048] The alcohol used in the raw material synthesis 2 in the present invention is represented by the general formula (5). In the general formula (5), R ³ has the same meaning as described above.

[0049] The amount of the alcohol is preferably from f to 0.5 to 200 monolayers, and more preferably (preferably ί to 2.0 to 150 monolayers, per 1 mol of 4,5-dihydroxy-2_imidazolidinone compound. It is.

[0050] The solid acid catalyst used in the raw material synthesis 2 in the present invention is not particularly limited as long as it is a solid having a Bronsted acid point. For example, clay minerals such as acidic clay; Name), Dowex (trade name), Diaion (trade name), Duolite (trade name), Levacit (trade name), Sumikaion (trade name), etc .; fluorination of naphthion, etc. Sulfonic acid resin; a force S including inorganic oxides such as silica alumina, zeolite and vanadium oxide, preferably a sulfonic acid type cation exchange resin. These solid acid catalysts may be used alone or in combination of two or more.

[0051] The amount of the solid acid catalyst used is 4, 5 dihydroxy-2 imidazolidinone compound lg On the other hand, it is preferably from ί to 0.001 to 1.0 g, and more preferably from 002 to 0.9 g.

[0052] The raw material synthesis 2 in the present invention may be carried out in the presence of a solvent other than alcohol, and is not particularly limited as long as it does not inhibit the reaction. For example, water; N, Amides such as N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Ureas such as 1,3_dimethylimidazolidinone; Ethers such as jetyl ether, diisopropyl ether, tetrahydrofuran and dioxane ; Aromatic hydrocarbons such as benzene, toluene and xylene; carboxylic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and propionitryl; and sulfoxides such as dimethyl sulfoxide. Preferably, nitriles, ureas, carboxylic acid esters, and aromatic hydrocarbons are used. In addition, you may use these solvents individually or in mixture of 2 or more types.

[0053] The amount of the solvent used is appropriately adjusted depending on the uniformity and stirring properties of the reaction solution, and is preferably 0 to 100 g, based on 4, 5-dihydroxy-1-2-imidazolidinone compound lg. Preferably it is 0-50g.

[0054] The raw material synthesis 2 in the present invention is performed, for example, by a method in which a solid acid catalyst, 4,5 dihydroxy-2 imidazolidinone compound and an alcohol are mixed and then reacted with stirring. The reaction temperature at that time is preferably 0 to 200 ° C, more preferably 10 to 100 ° C, and the reaction pressure is not particularly limited.

[0055] The 4,5 dialkoxy 2 imidazolidinone compound obtained in the raw material synthesis 2 in the present invention is, for example, neutralized, extracted, filtered, concentrated, distilled, recrystallized, crystallized, column chromatography after completion of the reaction. Isolation by a general method such as' force that can be purified 4, 5-dialkoxy _ 2 _ imidazolidinone compound is particularly useful for the next reaction (4,5-dialkoxy _ 2 _ The ability to be used continuously for the reaction of imidazolidinone compounds with hydrogen.

Example

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 (Synthesis of 4,5 dimethoxy-1,3 dimethyl-2 imidazolidinone: raw material synthesis Act 1)

Made of glass having an inner volume of 30ml with a stirrer and a thermometer, 1, 3-dimethyl urea 1.00g (ll. 3mmol), 40 mass ^_0/0 aqueous glyoxal 1. 65g (ll. 3mmol), scan sulfonic acid Type cation exchange resin (trade name; Dowex 50WX2) 0.2g and methanol 10ml (247mmol) were added and reacted at 60 ° C for 4.5 hours with stirring. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 1.50 g of 4,5-dimethoxy_1,3-dimethyl-2-imidazolidinone was produced (reaction yield). Rate; 76%).

Example 2 (Synthesis of 4,5-dimethoxy-1,3-dimethyl_2-imidazolidinone: raw material synthesis method 1)

Made of glass having an inner volume of 30ml with a stirrer and a thermometer, 1, 3-dimethyl urea 1.00g (ll. 3mmol), 40 mass ^_0/0 Guriokisanore solution 1. 65g (ll. 3mmol), scan sulfone 0.2 g of acid type cation exchange resin (trade name; Dowex M31) and 10 ml (247 mmol) of methanol were added and reacted at 60 ° C. for 4.5 hours with stirring. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 1.46 g of 4,5-dimethoxy 1,3-dimethyl-2-imidazolidinone was formed (reaction yield; 74%) .

Example 3 (Synthesis of 4,5 dimethoxy-1,3 dimethyl-2 imidazolidinone: raw material synthesis method 1)

In a glass container with an internal volume of 30 ml equipped with a stirrer and a thermometer, 1,3 dimethylurea (1.00 g, ll. 3 mmol), glyoxal trimer dihydrate (0, 95 g, 4.5 mmol), Phosphonic acid type cation exchange resin (trade name; Dowex M31) 0.2 g and methanol 10 ml (247 mmol) were added, and the mixture was reacted at 60 ° C. for 4.5 hours with stirring. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 1.65 g of 4,5 dimethoxy-1,1,3 dimethyl-1,2_imidazolidinone was produced (reaction yield). 84%).

Example 4 (Synthesis of 4,5_dibutoxy-1,3-dimethyl_2_imidazolidinone: raw material synthesis method 1)

Made of glass having an inner volume of 30ml with a stirrer and a thermometer, 1, 3-dimethyl urea 1.00g (ll. 3mmol), 40 mass ^_0/0 Guriokisanore solution 1. 65g (ll. 3mmol), scan sulfone Acid type cation exchange resin (trade name; Dowex 50WX2) 0.2g and n-butanol Nore 10 ml (109 mmol) was added, and the mixture was reacted at 60 ° C for 4.5 hours with stirring. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 1,02 g of 4,5-dibutoxy-1,3 dimethyl-2-imidazolidinone was produced (reaction yield; 35%) .

[0061] Reference Example 1 (Synthesis of 4,5-dihydroxy-1,3-dimethyl-1,2-imidazolidinone)

To a glass container having an internal volume of 1000 ml equipped with a stirrer, a thermometer and a dropping funnel, 290 g (2. Omol) of 40% by mass aqueous glyoxal solution and triethylamine were added (pH f of the reaction solution to 9). At the next level, the night temperature is 25-35. The force not kept at C S et al. After slowly adding a solution prepared by dissolving 176 g (2.0 mol) of 1,3_dimethylenourea in 176 ml of water, the mixture was reacted at the same temperature for 15 hours while stirring. —666.6 g of an aqueous solution containing dihydroxy-1,2-imidazolidinone was obtained.

[0062] To 333.3 g of the aqueous solution, 700 ml of jetyl carbonate was added, and water was subjected to azeotropic distillation (40 to 60 ° C, 2 to 13 kPa). The obtained white solid was filtered, dried under reduced pressure at 50 ° C, and 4,5-dihydroxy 1,3-dimethyl-2-imidazolidinone with a purity of 94.1% (absolute quantitative value by high performance liquid chromatography) 137 g were obtained (isolated yield based on 1,3 dimethylurea; 88.3

%).

Example 5 (Synthesis of 4,5 dimethoxy-1,3 dimethyl-2 imidazolidinone: raw material synthesis method 2)

In a 30 ml glass container equipped with a stirrer, thermometer and reflux condenser, 500 mg (3.4 mmol) of 4,5-dihydroxy-1,3-dimetholeimidazolidinone, sulfonic acid type cation exchange resin ( (Product name: Nafion) lOOmg and 5 ml of methanol were added and reacted at room temperature for 5 hours. After the completion of the reaction, the reaction solution was analyzed by gas chromatography (quantitative value by internal standard method). As a result, 540 mg of 4,5-dimethoxy-1,3-dimethyl-1,2-imidazolidinone was produced. (Reaction yield; 91%).

Example 6 (Synthesis of 4,5-dimethoxy-1,3-dimethyl_2_imidazolidinone: raw material synthesis method 2)

In a 30 ml glass container equipped with a stirrer, thermometer and reflux condenser, 500 mg (3.4 mmol) of 4,5-dihydroxy-1,3-dimethinoreimidazolidinone, sulfonic acid type cation exchange resin (Product name: Dowex 50WX2) Add lOOmg and 5ml methanol, The reaction was allowed to proceed for 16 hours at warm temperature. After completion of the reaction, the reaction solution was analyzed by gas chromatography (quantitative value by internal standard method). As a result, 571 mg of 4,5 dimethoxy 1,3 dimethyl-2-imidazolidinone was produced (reaction yield; 96%). .

Example 7 (Synthesis of 4,5-dimethoxy-1,3-dimethyl_2-imidazolidinone: raw material synthesis method 2)

In a 30 ml glass container equipped with a stirrer, thermometer and reflux condenser, 500 mg (3.4 mmol) of 4,5-dihydroxy-1,3-dimethylenomidazolidinone, sulfonic acid type cation exchange resin ( Trade name: Dowex 50WX2) 100 mg, 1 ml of methanol and 0.5 ml of water were added and reacted at room temperature for 5 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (quantitative value by internal standard method). As a result, 57 lmg of 4,5-dimethoxy-1,3-dimethyl_2-imidazolidinone was produced (reaction). Yield; 96%).

[0066] Example 8 (Synthesis of 1,3-dimethyl_2_imidazolidinone)

In a 100 ml stainless steel pressure vessel equipped with a stirrer and a thermometer, 4,5 dimethoxy-1,1,3 dimethyl-1,2 imidazolidinone 1.00 g (5.7 mmol), platinum one palladium / carbon 1 g and 10 ml of ethylene glycol were added, and the mixture was stirred at 150 ° C. for 6 hours in a hydrogen atmosphere (2.4 MPa). After completion of the reaction, the reaction mixture was analyzed by gas chromatography (internal standard method). As a result, 598 mg of 1,3 dimethyl-2-imidazolidinone was produced (reaction yield; 91%).

Example 9 (Synthesis of 1,3 dimethyl-2 imidazolidinone)

In a 100 ml stainless steel pressure vessel equipped with a stirrer and a thermometer, 4,5 dimethoxy-1,1,3 dimethyl-1,2 imidazolidinone 1.00 g (5.7 mmol), platinum one palladium / carbon 1 g and 10 ml of ethylene glycol were added, and the mixture was stirred at 50 ° C. for 6 hours in a hydrogen atmosphere (2.4 MPa). After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 605 mg of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 92%).

Example 10 (Synthesis of 1,3-dimethyl-2_imidazolidinone)

In a 100 ml stainless steel pressure-resistant vessel equipped with a stirrer and thermometer, 4, 5-dimethoxy-1,3-dimethyl-1,2-imidazolidinone 4.00 g (22.8 mmol), platinum 0.4 g of sulfur / carbon and 40 ml of water were added, and the mixture was stirred at 150 ° C for 6 hours in a hydrogen atmosphere (2.4 MPa). After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 2.39 g of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 92%).

[0069] Example 11 (Synthesis of 1,3-dimethyl-2_imidazolidinone)

In a glass container with an internal volume of 30 ml equipped with a stirrer, a thermometer and a reflux condenser, 500 mg (2.9 mmol) of 4,5-dimethoxy-1,3-dimethylenomidazolidinone, platinum-palladium / carbon 05 g and 5 ml of n_butyl alcohol were added, and the mixture was stirred at 100 ° C. for 6 hours in a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 291 mg of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 89%).

Example 12 (Synthesis of 4,5_dibutoxy-1,3-dimethyl_2_imidazolidinone: raw material synthesis method 2)

In a glass container with an internal volume of 30 ml equipped with a stirrer, thermometer, and reflux condenser, 500 mg (3.4 mmol) of 4,5-dihydroxy-1,3-dimethylenomidazolidinone, sulfonic acid type cation exchange resin (Product name: Dowex 50WX4) 50 mg and n-butyl alcohol 5 ml (55 mmol) were added and reacted at room temperature for 16 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (quantitative value by internal standard method). As a result, 813 mg of 4,5-dimethoxy-1,3-dimethylimidazolidinone was produced (reaction yield; 92%).

Example 13 (Synthesis of 4,5-dibutoxy-1,3-dimethyl-2-imidazolidinone: raw material synthesis method 2)

In a glass container with a capacity of 30 ml equipped with a stirrer, thermometer and reflux condenser, 4, 5-dihydroxy 1,3-dimethylol 2 _imidazolidinone 500 mg (3.4 mmol), sulfonic acid cation Exchange resin (trade name: Dowex 50WX4) lOOmg and 5 ml (55 mmol) of n_butyl alcohol were added and reacted at 50 ° C. for 5 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (quantitative value by internal standard method). As a result, 613 mg of 4,5-dimethoxy-1,3-dimethyl-1,2_imidazolidinone was produced. Reaction yield; 70%).

Example 14 (Synthesis of 4,5_dibutoxy_1,3-dimethyl-2-imidazolidinone: raw material synthesis method 2) In a glass container with a capacity of 300 ml equipped with a stirrer, thermometer and reflux condenser, 4,5-dihydroxy-1,3-dimethylimidazolidinone 20 g (137 mmol), sulfonic acid type cation exchange resin (product) Name: 2 g of Dowex 50WX4) and 200 ml (2.2 mol) of n-butyl alcohol were added and reacted at room temperature for 5 hours. After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 10 Zl), and as a colorless liquid, 27 g of 4,5_dibutoxy_1,3-dimethyl-2_imidazolidinone was added. Obtained (isolation yield; 76%).

[0073] The physical properties of 4,5_dibutoxy-1,3-dimethyl-2-imidazolidinone were as follows.

'H-NMRCDMSO-d, δ (ppm)); 0.93 (6H, t, J = 7.3 Hz), 1.32 to 1.45 (4H, m), 1 · 53 to 1.63 (4

H, m), 2.87 (6H, s), 3.39 to 3.51 (4H, m), 4.55 (2H, s)

CI-MS (m / e); 259 (M + l)

Example 15 (Synthesis of 1,3-dimethyl-2-imidazolidinone)

In a glass container with an internal volume of 30 ml equipped with a stirrer, thermometer and reflux condenser, 4,5-dibutoxy-1,3-dimethyl-2-imidazolidinone 500 mg (l.9 mmol), platinum monoparadium / carbon 0.05 g and 5 ml of n-butyl alcohol were added, and the mixture was stirred at 100 ° C for 6 hours in a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method), and as a result, 216 mg of 1,3-dimethyl-1,2-imidazolidinone was produced (reaction yield; 98%).

Example 16 (Synthesis of 1,3-dimethyl-2-imidazolidinone)

In a glass container with an internal volume of 30 ml equipped with a stirrer, thermometer and reflux condenser, 4,5-dibutoxy-1,3-dimethylol 2 _imidazolidinone 500 mg (l.9 mmol), noradium / carbon 05 g and 5 ml of n_butyl alcohol were added, and the mixture was stirred at 100 ° C. for 6 hours in a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 158 mg of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 72%).

Example 17 (Synthesis of 1,3-dimethyl_2-imidazolidinone)

In a 30 ml glass container equipped with a stirrer, thermometer and reflux condenser, 4, 5 —Dibutoxy-1,3-dimethyl-2-imidazolidinone 500 mg (l.9 mmol), platinum monopalladium / carbon 0.05 g and n-butyl alcohol 5 ml were added, and hydrogen atmosphere (normal pressure) at 50 ° C. Stir for 6 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method), and as a result, 216 mg of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 98%).

Example 18 (Synthesis of 1,3-dimethyl_2_imidazolidinone)

In a glass container with an internal volume of 30 ml equipped with a stirrer, thermometer and reflux condenser, 4, 5-dibutoxy-1,3-dimethinole 2_imidazolidinone 500 mg (l. 9 mmol), platinum monoparadium Z Carbon 0.05g and ethyl alcohol 5ml were added, and it stirred at 100 degreeC for 6 hours by hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction mixture was analyzed by gas chromatography (internal standard method). As a result, 212 mg of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 96%).

Example 19 (Synthesis of 1,3-dimethyl-2-imidazolidinone)

In a glass container with an internal volume of 30 ml equipped with a stirrer, thermometer and reflux condenser, 4,5-dibutoxy-1,3-dimethyl-2-imidazolidinone 500 mg (l.9 mmol), platinum-paradium / carbon 0.05 g and 5 ml of isopropyl alcohol were added, and the mixture was stirred at 100 ° C for 6 hours in a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, 210 mg of 1,3-dimethyl-2-imidazolidinone was produced (reaction yield; 95%).

Example 20 (Synthesis of 1,3-dimethyl-2-imidazolidinone)

In a glass container with an internal volume of 1000 ml equipped with a stirrer, thermometer and reflux condenser, 4, 5_dibutoxy-1,3-dimethyl-1,2_imidazolidinone 100 g (387 mmol), platinum 1 palladium / carbon ( Product name: ASCA2 (manufactured by YN Chemchem)) 10 g and 700 ml of n-butyl alcohol were added and stirred at 55 to 65 ° C. for 12 hours in a hydrogen atmosphere (normal pressure). After completion of the reaction, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The resulting concentrate was distilled under reduced pressure (90 ° C, 0.2 kPa) to obtain 33.7 g of 1,3-dimethyl-2-imidazolidinone as a colorless liquid (isolation yield; 76% ).

[0080] Example 21 (synthesis of 1,3-dimethyl_2_imidazolidinone) (Reaction A: Raw material synthesis method 2)

In a glass container with a capacity of 2000 ml equipped with a stirrer, thermometer and reflux condenser, 4,5-dihydroxy-1,3-dimethylimidazolidinone synthesized in Reference Example 130 (0.84 mol), sulfone 13 g of acid type cation exchange resin (trade name; Dowex 50WX2) and 1300 ml of n-butinoreanoreconole were allowed to react at room temperature for 17 hours. 4,5_dibutoxy-1,3-dimethyl-2 _A reaction solution containing imidazolidinone as a main component was obtained.

(Reaction

After filtration of the reaction solution, 13 g of platinum-palladium Z carbon (ASCA: 50% water-containing product) was added to the obtained filtrate, and the mixture was stirred at 60-80 ° C for 8 hours in a hydrogen atmosphere (normal pressure). Reacted. After completion of the reaction, the reaction solution was filtered and analyzed by gas chromatography (internal standard method). As a result, 83. l lg of 1,3-dimethyl-2-imidazolidinone was formed (reaction yield; 87% ). Next, the reaction solution was distilled under reduced pressure (100 to 110 ° C, 1.2 kPa) to obtain 70.55 g of 1,3 dimethylenoyl 2 imidazolidinone having a purity of 96% as a colorless transparent liquid (4, 5— (Dihydroxy-1,3-dimethylimidazolidinone-based isolated yield; 71%)

[0081] Reference Example 2 (Synthesis of 4,5 dihydroxy 1,3 dimethyl-2 imidazolidinone)

In Reference Example 1, the reaction was carried out under the same conditions as in Reference Example 1 except that cetyl carbonate was changed to butyl acetate. As a result, 133.18 g of 4,5 dihydroxy 1,3 dimethyl-2-imidazolidinone with a purity of 89.6% (absolute quantitative value by high performance liquid chromatography) was obtained (isolated yield based on 1,3 dimethylurea). 81.7%).

Industrial applicability

The present invention relates to a method for producing a 2_imidazolidinone compound and a 4,5-dialkoxy_2_imidazolidinone compound. 2_imidazolidinone compounds and 4,5_alkoxy-2_imidazolidinone compounds are useful compounds as raw materials and synthetic intermediates for pharmaceuticals and agricultural chemicals, for example.

Claims

The scope of the claims

[1] General formula (1) in the presence of a metal catalyst

(Where

(Where

R ² and R are as defined above)

2_ Method for producing imidazolidinone compound represented by

2. The method for producing a 2-imidazolidinone compound according to claim 1, wherein the metal catalyst contains at least one metal atom selected from the group consisting of palladium, platinum and nickel.

[3] General formula (3) in the presence of solid acid catalyst

R R

\ I

(3)

0 0

(Wherein R represents a hydrogen atom or a hydrocarbon group), a dicarbonyl compound represented by the general formula (4)

0

^R1 \ people (4)

NNHH (Wherein R ¹ and R ² represent hydrogen atoms or hydrocarbon groups which may be the same or different.) And the urea compound represented by the general formula (5)

R ³ 0H ( ⁵ )

(Wherein R ³ represents an alkyl group) and reacting with an alcohol represented by general formula (1) to produce a 4,5-dialkoxy_2_imidazolidinone compound represented by general formula (1) The method for producing a 2-imidazolidinone compound according to claim 1 or 2, further comprising:

In the presence of a solid acid catalyst, general formula (6)

(Where

R ² and R represent the same or different hydrogen atom or hydrocarbon group. 4,5-Dihydroxy _ 2 _ imidazolidinone compound represented by the general formula (5)

(Wherein R ³ represents an alkyl group), and further comprising producing a 4,5 dialkoxy-2 imidazolidinone compound represented by the general formula (1) by reacting with an alcohol represented by the general formula (1): A method for producing a 2-imidazolidinone compound according to claim 1 or 2.

[5] Claims for producing a 4,5-dialkoxy-2-imidazolidinone compound represented by the general formula (1) and reacting with hydrogen in the presence of a metal catalyst without isolation. Item 5. A method for producing an imidazolidinone compound according to Item 4.

[6] General formula (3) in the presence of solid acid catalyst

(Wherein R represents a hydrogen atom or a hydrocarbon), a dicarbonyl compound represented by the general formula (4)

(Wherein R ¹ and R ² represent hydrogen atoms or hydrocarbon groups which may be the same or different.) And the urea compound represented by the general formula (5)

R ³ 0H (5)

(Wherein R ³ represents an alkyl group), which comprises reacting an alcohol represented by the general formula (1)

0

R ¹

N N (1)

Three

^R3 ° R ⁷ OR

(Where

R ² , R and R ³ are as defined above. )

A method for producing a 4,5 dialkoxy-2 imidazolidinone compound represented by the formula:

[7] General formula (6) in the presence of solid acid catalyst

(6)

(Where

R ² and R each represent a hydrogen atom or a hydrocarbon group which may be the same or different. And 4,5 dihydroxy-2 imidazolidinone compounds represented by general formula (5)

R ³ 0H (5)

(Where

R ² , R and R are as defined above. )

A process for producing a 4,5 dialkoxy 2 imidazolidinone compound represented by the formula:

8. The method for producing a 4,5-dialkoxy 2-imidazolidinone compound according to claim 6 or 7, wherein the solid acid catalyst is a sulfonic acid type cation exchange resin.