JP2908043B2 - Method for producing 2-imidazolones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel process for producing 2-imidazolones from 1,2-diols and ureas. Since 2-imidazolones have a five-membered ring containing a urea skeleton and further have a carbon-carbon double bond in the five-membered ring, the fields of use thereof are wide. For example, in addition to being used as a monomer for homopolymerization or copolymerization, it is an important compound as an intermediate in producing agricultural chemicals or pharmaceuticals.

[0002]

2. Description of the Related Art 2-Imidazolones are generally obtained by a method comprising reacting a hydrochloride of .alpha.-aminoaldehyde, .alpha.-aminoketone or .alpha.-amino-.beta.-ketonate with cyanic acid or a method comprising condensation of acyloin with urea. Can be Furthermore, it is formed by hydrolysis of a dihydrouric acid derivative or a uracil derivative. For example, when hydrolyzing 7,9-dimethyldihydrouric acid with dilute sodium hydroxide, 1,3
-Dimethyl-2-imidazolone-4-carboxylic acid is produced, which is decarboxylated by heating to give 1,3-dimethyl-2-imidazolone (Large Organic Chemistry, Vol. 15, 221).
page).

Further, the anion obtained by deprotonating 1,3-dimethylimidazolium tosylate with sodium hydride is oxidized with molecular oxygen to form 1,3.
-Dimethyl-2-imidazolone is also known (JCS Chem. Comm., 1).
975, 334). As described above, the conventional method for producing 2-imidazolones is not an industrial method because a complicated synthesis route is required.

On the other hand, it has been reported that the reaction between ethylene glycol and N, N'-dimethylurea, which are the same raw materials as in the present invention, was carried out at 250 ° C. without using any catalyst. Dimethyl-2-imidazolidinone and 2-
No imidazolones are formed (Japanese Patent Application Laid-Open No. 58-15 / 1988)
0565).

[0005]

As described above, the conventionally known methods for producing 2-imidazolones cannot be said to be an industrial production method because a complicated synthesis step is required. An object of the present invention is to establish an industrial method for producing 2-imidazolones from a commercially available raw material in a one-step reaction.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to establish an industrial production method of 2-imidazolones. As a result, 1,2 that can be used industrially at low cost
-It has been found that when a diol and a urea are reacted in the presence of a catalyst, 2-imidazolones can be directly produced in a single reaction step, and the present invention has been completed.

That is, the present invention relates to a compound represented by the general formula (1): R ¹ CH (OH) CHR ² (OH) (1) (wherein R ¹ and R ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, Group or benzyl group,
1,2-diols represented by the following general formula (2): R ³ NHCONHR ⁴ (2) wherein R ³ and R ⁴ are a hydrogen atom, an alkyl Group, cycloalkyl group, aryl group or benzyl group,
A urea represented by the following general formula [Chemical Formula 2]:

[0008]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, which may be the same or different). Is a method for producing 2-imidazolones. The reaction between 1,2-diols and ureas gives 2
-The formation of imidazolones is a novel reaction which has never been known before and the present invention is the first example.

Hereinafter, the present invention will be described in more detail. Examples of 1,2-diols used in the method of the present invention include the following. Ethylene glycol, 1-phenyl-1,2-ethanediol, propylene glycol, 1-phenyl-1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 2,3-hexanediol, 3,4-hexanediol, 1,2-cyclopentanediol, 1,2-cyclohexanediol,
Compounds such as 1,2-diphenyl-1,2-ethanediol and 1-cyclohexyl-1,2-ethanediol can be exemplified.

Examples of the ureas used in the method of the present invention include the following. Urea, N,
N′-dimethylurea, N, N′-diethylurea, N,
N'-dipropyl urea, N, N'-diisopropyl urea, N, N'-di-n-butyl urea, N, N'-diisobutyl urea, N, N'-di-t-butyl urea, N, N '
N, N'-dialkyl ureas such as -dicyclopentyl urea, N, N'-dicyclohexyl urea, N, N'-dibenzyl ureas such as N, N'-dibenzyl urea, N, N '
N, N'-diphenylureas such as -diphenylurea can be exemplified. Further, N-ethyl-N'-methylurea, N-methyl-N'-propylurea, N-propyl-N'-n-butylurea, N-methyl-N'-phenylurea, N-methyl-N ' And ureas such as -benzylurea and N-phenyl-N'-benzylurea.

The ureas used in the method of the present invention and 1,2
The amount of the diol used is not particularly limited, but it is preferable to use the 1,2-diol in a ratio of 0.1 to 10 mol based on 1 mol of the urea.

The catalyst used in the method of the present invention is at least one selected from a platinum group metal and a compound containing a platinum group element, and examples thereof include the following. As a platinum group element in a metallic state, for example, a metal such as ruthenium, rhodium, palladium, osmium, iridium, and platinum, a metal black thereof, and a catalyst component containing these metal ions are supported on a carrier as described below, and then hydrogen is added. And those reduced with formaldehyde, hydrazine, or the like, and alloys or intermetallic compounds containing these metals are used. Further, the alloy or the intermetallic compound may be one of these platinum group metals, or another element, for example, selenium, tellurium,
Sulfur, antimony, bismuth, copper, silver, gold, zinc, tin, vanadium, iron, cobalt, nickel, mercury, lead,
It may contain thallium, chromium, molybdenum, tungsten, or the like. In addition, these catalyst components include activated carbon, graphite, silica, alumina, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, ion exchange resins, zeolites, molecular sieves, magnesium silicate, magnesia and other carriers. May be carried. Further, these carriers may be those treated with a basic substance.

On the other hand, compounds containing a platinum group element include, for example, halides such as ruthenium, rhodium, palladium, osmium, iridium and platinum; inorganic salts such as sulfates, nitrates, phosphates, borates; Organic acid salts such as acetates, oxalates and formates; cyanides; hydroxides; oxides; sulfides; metal salts containing anions such as nitro, cyano, halogen and oxalate ions; Examples include metal complex compounds such as ammonia, amines, phosphines, carbon monoxide, salts or complexes containing a chelating ligand, and the like; organometallic compounds having an organic ligand or an organic group.

Hereinafter, more specific examples of compounds containing a platinum group element will be given. As the compound containing ruthenium, for example, ruthenium dioxide, oxides such as ruthenium tetroxide, hydrates thereof, ruthenium chloride, ruthenium iodide, inorganic salts such as ruthenium nitrate, ruthenium acetate, ruthenium propionate and the like Organic acid salts, metal acid salts such as ammonium pentachlororuthenate (III), dodecacarbonyl triruthenium, tris (acetylacetonato) ruthenium, tris (hexafluoroacetylacetonato) ruthenium, cis-dichlorobis (2,2'- Bipyridine) ruthenium dihydrate, dichlorodicarbonylbis (triphenylphosphine) ruthenium, dichlorotricarbonylruthenium dimer, dichlorotris (triphenylphosphine) ruthenium, hydride (acetate) tris (trif Complex compounds and organometallic compounds such as phenylphosphine) ruthenium, bis (cyclopentadienyl) ruthenium, and tetra (dimethylsulfoxide) dichlororuthenium can be given.

Examples of compounds containing rhodium include rhodium oxides such as rhodium trioxide, hydrates thereof, inorganic salts of rhodium such as rhodium chloride, rhodium iodide, rhodium nitrate and rhodium sulfate, and acetic acid. Rhodium, organic acid salts of rhodium such as rhodium propionate, ammonium hexachlororhodate (III),
Metal salts such as trichlorohexamminerhodium (III), dodecacarbonyl tetrarhodium, hexadecacarbonyl hexarhodium, tris (acetylacetonato) rhodium, tris (hexafluoroacetylacetonato) rhodium, di-μ-chloro-tetra Rhodium carbonyl, chlorotris (triphenylphosphine) rhodium, trans- [chlorocarbonylbis (triphenylphosphine) rhodium], trans- [hydridocarbonyltris (triphenylphosphine) rhodium], dicarbonyl (2,4-pentadionato) rhodium , Tris (2,4-pentadionato) rhodium, di-μ-chlorobis (1,5-cyclooctadiene) dirhodium, di-μ-acetato-bis (1,5-cyclooctadiene)
Complex compounds such as dirhodium and organometallic compounds can be shown.

Examples of the compound containing palladium include palladium oxides such as palladium oxide, hydrates thereof, and inorganic salts of palladium such as palladium chloride, palladium bromide, palladium iodide, palladium nitrate and palladium sulfate. Organic acid salts of palladium, such as palladium acetate, palladium propionate, metal salts such as dichlorotetraamminepalladium, dinitrodiamminepalladium, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, dichloro (1,5-cyclooctadiene) ) Palladium, dichloro (norbornadiene) palladium, bis (acetylacetonato) palladium, di-μ-chloro-bis [(π-allyl) palladium], dichlorobis (triphenylphosphine) para Indium, bis [bis (1,2-
Diphenylphosphino) ethane] palladium, tetrakis (triphenylphosphine) palladium, bis (2
Complex compounds such as (4-pentadionato) palladium and organometallic compounds can be shown.

Examples of the osmium-containing compound include osmium oxides such as osmium tetroxide, hydrates thereof, inorganic salts of osmium such as osmium chloride and osmium nitrate, organic acid salts such as osmium acetate and hexadecane. Metal salts such as ammonium bromoosmate (IV), complex compounds and organometallic compounds such as triosmium dodecacarbonyl, osmium bis (cyclopentadienyl) osmium, osmium hydridebromotris (triphenylphosphine) osmium Can be done.

Examples of the compound containing iridium include, for example, inorganic salts of iridium such as iridium chloride, iridium nitrate and iridium sulfate; organic acid salts such as iridium acetate; hexachloroiridium (IV) acid hydrate; and hexachloroiridium ( IV) metal salts such as ammonium acid, dodecacarbonyltetrairidium, dicarbonyl (acetylacetonato) iridium, chlorocarbonylbis (triphenylphosphine) iridium, iodocarbonylbis (triphenylphosphine) iridium, hydridecarbonyltris (triphenyl) Complex compounds and organometallic compounds such as (phosphine) iridium and di-μ-chlorobis (1,5-cyclooctadiene) diiridium can be shown.

Examples of the compound containing platinum include, for example,
Oxides such as platinum dioxide, hydrates thereof, inorganic salts such as platinum dichloride, platinum tetrachloride, platinum iodide, platinum nitrate, and platinum sulfate; organic acid salts such as platinum acetate; hexachloroplatinic (IV) acid Hydrates, metal salts such as potassium hexachloroplatinate (IV), ammonium hexachloroplatinate (IV), bis (acetylacetonato) platinum, bis (hexafluoroacetylacetonato) platinum, cis-dinitrodiammineplatinum, cis -Dichlorobis (acetonitrile) platinum, dichlorobis (benzonitrile) platinum,
Dichloro (1,5-cyclooctadiene) platinum, dichloro (norbornadiene) platinum, dichlorobis (triphenylphosphine) platinum, dichlorotri-n-butylphosphineplatinum, dichloro (2,2′-bipyridine) platinum,
Complex compounds such as tetrakis (triphenylphosphine) platinum and organometallic compounds can be shown.

The amount of the catalyst used is urea 1.00.
It is 0.01 to 100 gram atoms, preferably 0.1 to 80 gram atoms, as a metal, per mole. In the method of the present invention, a ligand containing oxygen, sulfur, nitrogen, phosphorus, arsenic, antimony, bismuth, tin, or the like may be used as a promoter for the platinum group compound.

Examples of these ligands include acetylacetone, hexafluoroacetylacetone, 2,2,6,
6-tetramethylheptane-3,5-dione, benzo-
Oxygen-containing ligands such as 15-crown-5, 15-crown-5, 18-crown-6, 1,2-dimercapto-
Sulfur-containing ligands such as 6-methylbenzene and tetrathiafulvalene, 2,2′-bipyridine, 1,2-diaminocyclohexane, diethylenetriamine, ethylenediamine, 1,10-phenanthroline, N, N, N ′, N ′
-Tetramethylethylenediamine, N, N, N ', N'
Nitrogen-containing ligands such as tetramethylorthophenylenediamine, triphenylphosphine, tri-n-butylphosphine, triisopropylphosphine, triethylphosphine, bis (1,2-dimethylphosphino) ethane, bis (1,2- Phosphine-containing ligands such as diphenylphosphino) ethane, bis (1,3-diphenylphosphino) propane, cyclohexyldiphenylphosphine, triethylphosphite, and triphenylphosphite; bis (1,2-diphenylarsino) ethane; bis (Diphenylarsino) arsenic-containing ligands such as methane, methyldiphenylarsine, triphenylarsine, and triethylarsine; antimony-containing ligands such as tri-n-butylantimony and triphenylantimony; stannous chloride dihydrate; of It can be shown such as tin ligand. The amount of these ligands used is from 0.1 to 200 moles per gram atom of metal of the catalyst.

The method of the present invention can be carried out without using a solvent, but can be carried out in a solvent if necessary. As the solvent to be used, any solvent that does not adversely affect the reaction can be used. In the method of the present invention, examples of the solvent preferably used include, for example, heptane,
Saturated and aromatic hydrocarbons such as octane, cyclohexane, decalin, tetralin, kerosene, benzene, toluene, xylene, durene, hexamethylbenzene, and halogens such as chloropentane, o-dichlorobenzene, p-chlorotoluene, and fluorobenzene Hydrocarbons, ethers such as dioxane, tetrahydrofuran, ethyl ether, anisole, phenyl ether, diglyme, tetraglyme, 18-crown-6, esters such as methyl acetate, ethyl butyrate, methyl benzoate, γ-butyrolactone, and acetone , Acetophenone, benzophenone and other ketones, N-methylpyrrolidine-2-
N-substituted amides such as ON, N-ethylpyrrolidin-2-one, N, N-dimethylacetamide, N-methylpiperidone, hexamethylphosphoric triamide;
Tertiary amines such as N-diethylaniline, N-methylmorpholine, pyridine and quinoline; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide;
Examples include urea derivatives such as 1,3-dimethyl-2-imidazolidinone, phosphine oxides such as tributylphosphine oxide, and silicon oil. Among them, particularly preferred solvents include saturated hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and phosphine oxides. These solvents can be used alone or as a mixed solvent.

In the method of the present invention, the reaction temperature is 80 to 240.
C., preferably at 100-220.degree. Reaction temperature 8
Below 0 ° C., the reaction is extremely slow. On the other hand, when the temperature exceeds 240 ° C., the decomposition of ureas used as a raw material increases remarkably. In the present invention, the reaction pressure is performed at the autogenous pressure. The pressure in this case differs depending on the type of the solvent used, but is usually 50 k
g / cm ² gauge or less. The reaction pressure may be increased by an inert gas such as argon, nitrogen or helium if necessary.
/ Cm ² gauge or less.

The reaction time depends on the reaction temperature, the type of catalyst,
Depending on the type of raw materials used, etc., usually 0.05
-100 hours, preferably 0.1-80 hours. The method of the present invention can be carried out by any of a batch system, a semi-continuous system and a continuous system. The 1,2-diols, ureas, catalysts, liquid media, and the like may be added to the reactor in a batch mode or may be supplied in a semi-continuous or continuous mode. The product can be taken out by a known method, for example, a method such as distillation or extraction, and unreacted 1,2-diols and ureas are again circulated to the reactor together with a catalyst and a liquid medium. Can be used.

[0025]

EXAMPLES The method of the present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

[Example 1] A stainless steel autoclave having an inner volume of 50 ml (made by Yuasa Giken, US
After replacing 316) with argon gas, 0.19 g of dichlorotris (triphenylphosphine) ruthenium (0.2 mg atom as ruthenium), 0.44 g (5.0 mmol) of 1,3-dimethylurea, and 0.1 g of ethylene glycol were added. 62 g (10.0 mmol) and 4 ml of tetrahydrofuran as a solvent were added, and the inside of the autoclave was replaced with argon gas. Next, the autoclave was heated under stirring, and when the internal temperature reached 180 ° C., the reaction was carried out at a constant temperature for 6 hours. After the completion of the reaction, the autoclave was cooled to room temperature, and then the autoclave was opened to take out a reaction mixture containing a catalyst, a solvent and a reaction product. As a result of quantifying the reaction solution by gas chromatography, the conversion of 1,3-dimethylurea was 84%,
The selectivity for 3-dimethyl-2-imidazolone was 47.6% based on 1,3-dimethylurea.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 150 ° C. As a result, the conversion of 1,3-dimethylurea was 72
%, Selectivity for 1,3-dimethyl-2-imidazolone was 48.6% based on 1,3-dimethylurea.

Example 3 A reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed to 120 ° C. As a result, the conversion of 1,3-dimethylurea is 10
%, Selectivity for 1,3-dimethyl-2-imidazolone was 80.0% based on 1,3-dimethylurea.

Example 4 In Example 1, the amount of ethylene glycol used was changed to 1.24 g (20.0 mmol).
The reaction was carried out in the same manner as in Example 1 except that the reaction was changed to. As a result, the conversion of 1,3-dimethylurea was 63% and 1,3
The selectivity for -dimethyl-2-imidazolone was 33.3% based on 1,3-dimethylurea.

Example 5 In Example 1, 0.05 g of ruthenium trichloride hydrate was used as a catalyst instead of dichlorotris (triphenylphosphine) ruthenium.
(0.2 mmol) and triphenylphosphine 0.1.
The reaction was carried out in the same manner as in Example 1 except that 16 g (0.6 mmol) was used. As a result, the conversion of 1,3-dimethylurea was 79%, and the selectivity of 1,3-dimethyl-2-imidazolone was 45.0% based on 1,3-dimethylurea.

[Embodiment 6] In Embodiment 1, 1,3-
1,6-diphenyl urea 1.06 instead of dimethyl urea
The reaction was carried out in the same manner as in Example 1 except that g (5.0 mmol) was used. As a result, the conversion of 1,3-phenylurea was 85%, and the selectivity of 1,3-diphenyl-2-imidazolone was 61.3% based on 1,3-diphenylurea.

Example 7 In Example 1, 0.45 g of 2,3-butanediol was used instead of ethylene glycol.
The reaction was carried out in the same manner as in Example 1 except that (5.0 mmol) was used. As a result, the conversion of 1,3-dimethylurea was 100%, and the selectivity of 1,3,4,5-tetramethyl-2-imidazolone was 55% based on 1,3-dimethylurea.
%Met.

Example 8 A reaction was carried out in the same manner as in Example 7, except that the reaction time was changed from 6 hours to 24 hours. As a result, the conversion of 1,3-dimethylurea was 100% and 1,3,4,5-tetramethyl-2
-Selectivity for imidazolone was 62% based on 1,3-dimethylurea.

[Embodiment 9] In Embodiment 8, 2,3-
The reaction was carried out in the same manner as in Example 8, except that the amount of butanediol used was changed to 0.90 g (10.0 mmol).
As a result, the conversion of 1,3-dimethylurea was 100%.
The selectivity of 1,3,4,5-tetramethyl-2-imidazolone was 73% based on 1,3-dimethylurea.

EXAMPLE 10 In Example 1, 0.158 g (0.2 mmol) of dichlorobis (triphenylphosphine) platinum and stannous chloride dihydrate were used as catalysts instead of dichlorotris (triphenylphosphine) ruthenium. The reaction was carried out in the same manner as in Example 1 except that 0.045 g (0.2 mmol) of the product was used. as a result,
The conversion of 1,3-dimethylurea was 75%, and the selectivity of 1,3-dimethyl-2-imidazolone was 40.5% based on 1,3-dimethylurea.

Example 11 In Example 1, the catalyst was 0.094 g of dichlorobis (benzonitrile) platinum.
(0.2 mmol) and stannous chloride dihydrate 0.0
The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 45 g (0.2 mmol). As a result, the conversion of 1,3-dimethylurea was 81%, and the selectivity of 1,3-dimethyl-2-imidazolone was 53.3% based on 1,3-dimethylurea.

[0037]

Industrial Applicability According to the present invention, 2-imidazolones can be produced in a one-step reaction directly from 1,2-diols and ureas which can be industrially used at low cost. large.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ identification symbol FI // C07B 61/00 300 C07B 61/00 300 (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 233/70

Claims (2)

(57) [Claims] 1. A compound represented by the general formula (1): R ¹ CH (OH) CHR ² (OH) (1) wherein R ¹ and R ² are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a benzyl group. And
1,2-diols represented by the following general formula (2): R ³ NHCONHR ⁴ (2) wherein R ³ and R ⁴ are a hydrogen atom, an alkyl Group, cycloalkyl group, aryl group or benzyl group,
Urea compounds represented by the following general formulas [Chemical Formula 1], characterized in that they are reacted with each other in the presence of a catalyst. (Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, which may be the same or different). A method for producing 2-imidazolones. 2. The method according to claim 1, wherein the catalyst is at least one selected from a platinum group metal and a compound containing a platinum group element.