JP2003212855A - Method for producing 1,3-dialkyl-2-imidazolidinones - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing 1,3-dialkyl-2-imidazolidinones in high yield with high efficiency. <P>SOLUTION: This method for producing the 1,3-dialkyl-2-imidazolidinones comprises mixing a first component composed of 3-alkyl-2-oxazolidinones with a second component composed of at least one or more kinds of (A) carbon dioxide and a monoalkylamine, (B) a carbon dioxide compound of the monoalkylamine and (C) a 1,3-dialkylurea, heating and reacting the resultant mixture at ≥50°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1,3-dialkyl-2-imidazolidinones.

1,3-Dialkyl-2-imidazolidinones are compounds having a wide range of uses as aprotic polar solvents and the like. For example, solvent for resin such as polyamide, polyester, polyvinyl chloride or phenol resin,
It is a useful compound used as a solvent for various organic synthesis reactions, an extraction solvent for extracting aromatic hydrocarbons from a hydrocarbon mixture, and the like. Of these, 1,3-dimethyl-
2-Imidazolidinone (hereinafter, abbreviated as DMI in some cases) has particularly high durability against a strong alkali, and is particularly useful because it hardly decomposes even when heated with an alkali metal hydroxide solution. It is also used as a solvent for the dehalogenation reaction of.

[0003]

2. Description of the Related Art Conventionally, as a method for producing 1,3-dialkyl-2-imidazolidinones, for example, a method of reacting N, N'-dimethylethylenediamine with trichloromethylchloroformate (JP-A-53-73561). No.), a method of reacting N, N'-dimethylethylenediamine with carbon dioxide (JP-A-57-175170), and reacting N, N'-dimethylethylenediamine with phosgene in the presence of water and a dehydrochlorinating agent. Method (JP-A-61)
-109772, JP-A-61-172862), a method of reacting N, N'-dialkylethylenediamine and urea in a polar solvent (JP-A-7-2522).
30), various methods using N, N'-dialkylethylenediamine as a raw material have been proposed. As a method for producing N, N'-dialkylethylenediamines used as the raw material, for example, N, N'-dimethylethylenediamine, a method obtained from ethylene dichloride and monomethylamine (JP-A-57-120570) is known. However, in this method, a large amount of salt contaminated with organic compounds is produced as a by-product and its treatment becomes a problem.

A method of reacting ethylene glycol and monomethylamine in the presence of a ruthenium-triphenylphosphine-based homogeneous catalyst (J. Organom).
etallic Chem. , 407, 97, 19
1991), it is difficult to recover and recycle a homogeneous noble metal catalyst in industrial production. Therefore N,
1,3 made from N'-dialkylethylenediamine
It is difficult to say that the method for producing -dialkyl-2-imidazolidinone is an ideal method.

Further, a method of reducing 2-imidazolidinone and formaldehyde in the presence of a hydrogenation catalyst (Japanese Patent Laid-Open Publication No. 6-58242).
No. 0-243071), a method of catalytically reducing a dialkyl ether of N, N′-hydroxymethylimidazolidinone (Japanese Patent Publication No. 60-3299), and the like, the raw materials used in these methods are ethylenediamine. Since it is manufactured from, it has the same problem as above, and its process is long and unrealistic.

As another method, a method of reacting an alkylamine such as N-alkylmonoethanolamine and monomethylamine with carbon dioxide, an alkylamine salt of alkylcarbamic acid, or a 1,3-dialkylurea (JP-A-57-57) No. 98268), a method of reacting ethylene glycol with carbon dioxide and monomethylamine under high temperature and high pressure (JP-A-59-155364),
A method of reacting an alkylene carbonate and a monoalkylamine (Japanese Patent Publication No. 10-502917) is disclosed. These production methods have a problem that the production efficiency of 1,3-dialkyl-2-imidazolidinones is low because of the reaction for a long time, and have not reached the industrial level yet.

[0007]

An object of the present invention is to provide a method for producing 1,3-dialkyl-2-imidazolidinones with high efficiency and high yield.

[0008]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a method for producing 1,3-dialkyl-2-imidazolidinones with high efficiency and high yield, and found that 3-alkyl-2-oxazolidinone The first component consisting of
(A) Monoalkylamine, (B) monoalkylamine carbon dioxide compound, and (C) 1,3-dialkylurea are mixed with at least one second component and heated to 50 ° C or higher. It was found that 1,3-dialkyl-2-imidazolidinones can be produced with high efficiency and high yield by carrying out the reaction, and thus completed the present invention.

That is, the present invention uses the formula (1)

[0010]

[Chemical 5]

3-alkyl-2-oxazolidinones represented by the formula: wherein R ¹ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 6 carbon atoms. And the following (A)-
(C) (A) Formula (2)

[0012]

[Chemical 6]

(In the formula, R ³ represents an alkyl group having 1 to 6 carbon atoms), (B)
Carbon dioxide compound of monoalkylamine represented by the formula (2), (C) formula (3)

[0014]

[Chemical 7]

A 1,2-dialkylurea represented by the formula (wherein R ³ is defined as above) is mixed with a second component of at least one kind, and the mixture is heated to 50 ° C.
The reaction is performed by heating to the above formula (4)

[0016]

[Chemical 8]

(In the formula, R ¹ , R ² and R ³ are respectively defined as above.) A method for producing 1,3-dialkyl-2-imidazolidinones.

It is preferable to carry out the reaction in the presence of carbon dioxide. R ¹ is hydrogen, R ² and R ³ represent a methyl group, and the 1,3-dialkyl-2-imidazolidinones produced are 1,3-dimethyl-2-imidazolidinone. preferable.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The method of the present invention is represented by the formula (1):
A first component comprising an alkyl-2-oxazolidinone, and the following (A) to (C) (A) a monoalkylamine represented by formula (2), (B)
A carbon dioxide compound of a monoalkylamine represented by the formula (2) and a second component comprising at least one of (C) 1,3-dialkylurea represented by the formula (3) and 50. The mixture is heated to a temperature of not less than 0 ° C. and reacted to produce a 1,3-dialkyl-2-imidazolidinone represented by the formula (4).

3 used as a raw material in the method of the present invention
Examples of -alkyl-2-oxazolidinones include 3-methyl-2-oxazolidinone and 3-ethyl-
2-oxazolidinone, 3-propyl-2-oxazolidinone, 3- (1-methylethyl) -2-oxazolidinone, 3-butyl-2-oxazolidinone, 3- (1,
1-dimethylethyl) -2-oxazolidinone, 3-pentyl-2-oxazolidinone, 3-hexyl-2-oxazolidinone, 3-cyclohexyl-2-oxazolidinone, 3,5-dimethyl-2-oxazolidinone, 3
-Ethyl-5-methyl-2-oxazolidinone, 5-methyl-3-propyl-2-oxazolidinone, 5-methyl-3- (1-methylethyl) -2-oxazolidinone, 3-butyl-5-methyl-2-oxazolidinone ,
3-cyclohexyl-5-methyl-2-oxazolidinone, 5-ethyl-3-methyl-2-oxazolidinone,

3-Butyl-5-ethyl-2-oxazolidinone, 3- (1,1-dimethylethyl) -5-ethyl-2-oxazolidinone, 5- (1,1-dimethylethyl) -3-methyl-2 -The substituent represented by R ¹ such as oxazolidinone is hydrogen or a chain or cyclic alkyl group having 1 to 6 carbon atoms, and the substituent represented by R ² is an alkyl group having 1 to 6 carbon atoms 3-alkyl-
2-oxazolidinones are mentioned, and among these, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, or 1,3,4-trimethyl-obtained as a product. Since 2-imidazolidinone has a wide range of uses, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, or 3,5-dimethyl-2-oxazolidinone is preferable,
More preferred is 3-methyl-2-oxazolidinone.

As these 3-alkyl-2-oxazolidinones, commercially available products can be used as they are, or they can be used after purification such as distillation.

As the monoalkylamine represented by the formula (2), which is one of the second components in the method of the present invention,
For example, monomethylamine, monoethylamine, mono (n-propyl) amine, mono (iso-propyl) amine, mono (n-butyl) amine, mono (sec-butyl) amine, mono (iso-butyl) amine, mono ( t
ert-butyl) amine, mono (n-amyl) amine,
Mono (1-methylbutyl) amine, mono (2-methylbutyl) amine, mono (iso-amyl) amine,

Mono (tert-amyl) amine, mono (neo-pentyl) amine, mono (1,2-dimethylpropyl) amine, mono (1-ethylpropyl) amine, mono (n-hexyl) amine, or monocyclohexyl. Examples thereof include monoalkylamines having 1 to 6 carbon atoms in the chain or cyclic alkyl group represented by R ² such as amine. Of these, 1,3 obtained as a product
-Dimethyl-2-imidazolidinone, or 1,3-
Since diethyl-2-imidazolidinones have a wide range of uses, monomethylamine or monoethylamine is preferable, and monomethylamine is more preferable.

The carbon dioxide compound of monoalkylamine, which is one of the second components in the method of the present invention, is
Examples thereof include monoalkylamine carbonate, monoalkylamine hydrogencarbonate, and alkylcarbamate.

The carbon dioxide compound of these monoalkylamines can be used as a solution such as a solid or an aqueous solution, or can be used as a combination of components which form these carbon dioxide compounds in the reaction system.

Further, the 1,3-dialkylurea represented by the formula (3), which is one of the second components in the method of the present invention, is, for example, 1,3-dimethylurea or 1,3-diethylurea. Urea, 1,3-di (n-propyl) urea, 1,3
-Di (iso-propyl) urea, 1,3-di (n-butyl) urea, 1,3-di (sec-butyl) urea, 1,3
-Di (iso-butyl) urea, 1,3-di (tert-
Butyl) urea, 1,3-di (n-amyl) urea, 1,3
-Di (1-methylbutyl) urea, 1,3-di (2-methylbutyl) urea, 1,3-di (iso-amyl) urea,
1,3-di (tert-amyl) urea, 1,3-di (n
eo-pentyl) urea, 1,3-di (1,2-dimethylpropyl) urea, 1,3-di (1-ethylpropyl) urea,

1,3-di (n-hexyl) urea, or
R such as 1,3-dicyclohexylurea ²Represented by
1,3-Dialkylurea having 1 to 6 carbon atoms in the kill group
Is mentioned. Of these, obtained as a product
1,3-dimethyl-2-imidazolidinone, or
1,3-diethyl-2-imidazolidinone is widely used
1,3-Dimethylurea or 1,3-
Diethylurea is preferred, more preferably 1,3-dimme
Chilurea.

Commercially available products of these 1,3-dialkylureas can be used as they are or as a solution such as an aqueous solution, or these 1,3 dialkylureas can be used in the reaction system.
It can also be used as a combination of components that produce a dialkyl urea.

In the method of the present invention, the amount of the second component used in the reaction is not particularly limited, but the number of moles of monoalkylamine contained in the second component,
The number of moles of the monoalkylamine component in the carbon dioxide compound of the monoalkylamine and twice the number of moles of the 1,3-dialkylurea are usually 0.2 times the mole number of the 3-alkyl-2-oxazolidinones. The range is preferably 1 to 200 times, more preferably 0.5 to 80 times, still more preferably 1.0 to 40 times. If less than 0.1 times, 1,3-dialkyl-
It is disadvantageous in that the yield of 2-imidazolidinones tends to decrease, and when it exceeds 200 times, it is disadvantageous in that the volumetric efficiency of the reactor tends to decrease.

In the method of the present invention, the reaction system can be replaced with gas or pressurized. The gas used for this purpose is not particularly limited, and may be an inert gas such as nitrogen or argon, and it is more preferable to carry out the reaction in the presence of carbon dioxide. By using carbon dioxide, 1,3
-The production efficiency of dialkyl-2-imidazolidinones is improved. The carbon dioxide used is carbon dioxide, liquid carbon dioxide,
Solid carbonic acid or supercritical carbon dioxide can also be used.

The amount of carbon dioxide used in this reaction is not particularly limited, but is the number of moles of carbon dioxide, the number of moles of carbon dioxide component in the carbon dioxide compound of monoalkylamine, and 1,3- The sum of the number of moles of dialkyl urea is usually 0.3 to 200 times, and more preferably 1 to 100 times the number of moles of 3-alkyl-2-oxazolidinones used. . If less than 0.3 times, 1,3-dialkyl-
It is disadvantageous in that the yield of 2-imidazolidinones tends to decrease, and if it exceeds 200 times, it is disadvantageous in that the volumetric efficiency of the reactor tends to decrease.

The reactor used in the method of the present invention is not particularly limited, but at least a part of the inner wall of the reactor is composed of a metal containing titanium or zirconium and / or an oxide thereof. By using the existing reactor, 1,3-dialkyl-2 can be obtained in high yield.
-It is possible to produce imidazolidinones. As such a reactor, for example, one in which the entire reactor is made of a metal containing titanium or zirconium, or at least a part of the inner wall of the reactor is coated with a metal containing titanium or zirconium or an oxide thereof The inner wall of the reactor may be coated with inorganic glass. The metal containing titanium or zirconium is, for example, JIS standard 1 to 4 industrial pure titanium, titanium corrosion-resistant alloy such as Ti-0.15Pd, Ti-5Ta or Ti-0.3Mo-0.8Ni, Ti-2.5. Sn, Ti-5Al-2.5Sn, Ti-5Al-2.5Sn (E
LI), Ti-2.5Cu, Ti-2O-1N-5Fe, Ti-5Ni-0.5Ru, Ti-0.5P
α-3 type titanium alloy such as d-3Co or Ti-5.5Al-3.5Sn-3Zr-1Nb-0.3Mo-0.3Si, Ti-8Al-1Mo-1V, Ti-2.25Al-11Sn-5Zr-
1Mo-0.2Si, Ti-6Al-2Sn-4Zr-2Mo,

Ti-5Al-5Sn-2Zr-2Mo-0.25Sn, Ti-6Al-2Nb-
1Ta-0.8Mo, Ti-6Al-5Zr-0.5Mo-0.2Si or Ti-4.5Al-3V
-2Fe-2Mo and other near-alpha type titanium alloys, Ti-5Al-2Cr-1Fe, Ti-5
Al-5Sn-5Zr-2Cr-1Fe, Ti-4Al-4Mn, Ti-3Al-2.5V, Ti-6A
l-4V, Ti-6Al-4V (ELI), Ti-6Al-6V-2Sn, Ti-6Al-2Sn-4Z
r-6Mo, Ti-7Al-4Mo, Ti-5Al-2Zr-4Mo-4Cr, Ti-6Al-1.7F
e-0.1Si, Ti-6.4Al-1.2Fe, Ti-15Zr-4Nb-2Ta-2Pd, Ti-6
Α + β type titanium alloy such as Al-7Nb or Ti-8Mn, Ti-13V-1
1Cr-3Al, Ti-15Mo-5Zr, Ti-15Mo-0.2Pd, Ti-15V-3Cr-3S
n-3Al, Ti-20V-4Al-1Sn, Ti-22V-4Al or Ti-16V-4Sn-
Β-type titanium alloy such as 3Al-3Nb, Ti-10V-2Fe-3Al or Ti-
Examples include near-β type titanium alloys such as 9.5V-2.5Mo-3Al, zirconium alloys such as zircaloy-2, zircaloy-4, Zr-2.5Nb and ozenite. Among these metals, a metal containing titanium is preferable, and industrially pure titanium or titanium corrosion-resistant alloy is more preferable.

The embodiment of the reaction in the method of the present invention is not particularly limited, and any method may be used as long as the raw materials used can be effectively mixed with and brought into contact with other raw materials. Either a semi-batch type or a continuous flow type may be used. For example, a method of charging all the raw materials into a reactor all at once, a method of continuously or intermittently supplying the other raw material to at least one raw material, a method of continuously or intermittently supplying all the raw materials, and the like. Can be used.

The reaction in the method of the present invention is carried out by heating at 50 ° C. or higher. The heating temperature is preferably 50 to 400 ° C, more preferably 100 to 300 ° C.
Is. When it is lower than 50 ° C, it is disadvantageous in that the production efficiency is low, and when it is higher than 400 ° C, it is disadvantageous in that the yield of 1,3-dialkyl-2-imidazolidinones tends to be lowered. Is.

The reaction time varies depending on the amount of raw materials used, the reaction temperature, etc. and is not uniform, but the reaction time is usually 2
It is preferably within 0 hour, more preferably 0.01 to 15 hours, further preferably 0.1 to 10 hours. When shorter than 0.1 hour, 1,3-dialkyl-2
-It is disadvantageous in that the yield of imidazolidinones tends to decrease, and is longer than 20 hours, it is disadvantageous in that the reaction volume efficiency tends to deteriorate. The pressure during the reaction is usually preferably in a pressurized state, more preferably higher than atmospheric pressure and 50 MPa or less, further preferably 0.2 to 20 MPa.

The reaction in the method of the present invention may be carried out without a solvent, or in some cases a solvent may be used. Any solvent may be used as long as it is inert to the reaction substrate under the reaction conditions,
Water, hydrocarbons, ethers, amides, cyclic ureas, supercritical carbon dioxide, etc. are preferably used, and among these, 1,3-dialkyl-2-imidazolidinone, which is the same as water or the product, is used. It is more preferable to use. Water 1,
3-dialkyl-2-imidazolidinones are 1,3-
It is advantageous in that the production efficiency of the dialkyl-2-imidazolidinones is increased. These solvents can be used alone or in combination of two or more, and the reaction can be carried out in a multi-phase system having two or more phases depending on the solvent used.

The amount of these solvents to be used is not particularly limited, but it is sufficient that at least a part of the starting materials used is dissolved, and the amount of the starting materials usually used is 3-alkyl-2-oxazolidinone. On the other hand, it is preferably 100 mass ratio or less, and more preferably 50 mass ratio or less. 10
When it is more than 0 mass ratio, it is disadvantageous in that the volume efficiency tends to decrease.

In the method of the present invention, a catalyst or an additive may be used in order to further increase the yield or the reaction rate.

In the method of the present invention, the desired product, 1,3-dialkyl-2-imidazolidinone, can be obtained by treating the reaction product solution according to a conventional method such as distillation or crystallization, if necessary. .

[0043]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example In an autoclave made of industrial pure titanium of JIS standard 2 type having an internal volume of 80 ml, 6.07 g (60 mmol) of 3-methyl-2-oxazolidinone and 53% by weight methylamine carbamate methylamine salt aqueous solution 36. 0g was charged. After replacing the gas phase part with nitrogen, 5.3 g of carbon dioxide was charged.

The mixture was heated from the outside of the autoclave and reacted with stirring at an inner temperature of 200 ° C. and a maximum pressure of 8 MPa for 3 hours. After cooling the autoclave to room temperature, the reaction solution was taken out and analyzed by gas chromatography. 3-
The conversion rate of methyl-2-oxazolidinone was 99%, and the DMI yield based on the charged 3-methyl-2-oxazolidinone was 86%.

[0046]

According to the method of the present invention, 3-alkyl-2
A first component composed of oxazolidinones, and a second component composed of at least one of (A) monoalkylamine, (B) monoalkylamine carbon dioxide compound, and (C) 1,3-dialkylurea. By heating to 50 ° C or higher to react with 1,3-
Dialkyl-2-imidazolidinones can be produced.

Claims (3)

[Claims] 1. Formula (1): (In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 6 carbon atoms.) A 3-alkyl-2-oxazolidinone group represented by One component and the following (A) to (C) (A) formula (2) (In the formula, R ³ represents an alkyl group having 1 to 6 carbon atoms), (B) a carbon dioxide compound of the monoalkylamine represented by the formula (2), (C) Formula (3) (In the formula, R ³ is defined as above.) 1,3-dialkylurea represented by at least one kind of second component is mixed and heated to 50 ° C. or higher. To react with the compound of formula (4) (In the formula, R ¹ , R ² and R ³ are each defined as above.) 1,3-dialkyl-2-
Method for producing imidazolidinones. 2. The method according to claim 1, wherein the reaction is carried out in the presence of carbon dioxide. 3. A 1,3-dialkyl-2-produced wherein R ¹ is hydrogen and R ² and R ³ represent a methyl group.
The method according to claim 1 or 2, wherein the imidazolidinone is 1,3-dimethyl-2-imidazolidinone.