JPH07206828A - 1,3-dialkyl-4-methyl-2-imidazolidinone - Google Patents

Abstract

PURPOSE:To obtain a new 1,3-dialkyl-4-methyl-2-imidazolidinone useful as a sparingly water-soluble aprotic polar solvent, a solvent for synthetic reactions and polymerizations, an extraction solvent, a detergent, etc. CONSTITUTION:The objective compound, a 1,3-dialkyl-4-methyl-2-imidazolidinone of the formula (R is propyl or butyl), e.g. 1,3-dibutyl-4-methyl-2-imidazolidinone. This compound of the formula can be obtained, for example, by preparing an N,N'-dialkyl-1,2-diaminopropane from 1,2-dichloropropane and an alkylamine followed by reaction of the product with urea, phosgene or CO2 and then carrying out e.g. cyclization. This compound of the formula also gets sparingly soluble to water by introducing a methyl group into the carbon atom at the 4-site.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (1)

[0002]

[Chemical 2] [In the formula, R represents a propyl group or a butyl group. ] It is related with 1,3-dialkyl-4-methyl-2-imidazolidinone, which is a novel poorly water-soluble aprotic polar substance. The compound is a substance useful as a solvent for synthesis reaction, a polymerization reaction, an extraction solvent, a detergent and the like.

[0003]

2. Description of the Related Art As aprotic polar substances, water-soluble substances such as 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone are known. These compounds are useful as solvents. In particular, it is an excellent solvent for polymer compounds such as polyamide, polyvinyl chloride, polyvinyl alcohol, polystyrene, polyurethane, and phenol resin, and is also used as a solvent for many organic reactions.

[0004]

When a water-soluble aprotic polar substance is used as a reaction solvent, it has an excellent solvent effect, but since it is water-soluble, it is separated and recovered in the post-treatment after the reaction and the purification step. However, the operation was complicated and the recovery rate from the aqueous solution was low, which was a problem. It is an object of the present invention to provide a novel compound which is an aprotic polar substance and also has poorly water-soluble physical properties in order to overcome the above-mentioned drawbacks.

[0005]

Means for Solving the Problems As a result of diligent studies on the development of a poorly water-soluble aprotic polar substance, the present inventors have found that the 1- and 3-positions of 1,3-dialkyl-2-imidazolidinone.
It was found that the object can be achieved by making the alkyl group at the 4-position a propyl group or a butyl group and further introducing a methyl group at the 4-position carbon, and completed the present invention. That is, the present invention has the general formula (1)

[0006]

[Chemical 3]

[In the formula, R represents a propyl group or a butyl group. ] 1,3-dialkyl-4-methyl-2-imidazolidinone represented by the following is provided.

1,3-Dialkyl (provided that it is propyl or butyl) -4-methyl-2-imidazolidinone is first prepared from 1,2-dichloropropane and an alkylamine to obtain N, N'-dialkyl-1,2-diamino. It can be obtained by a method of producing propane, reacting it with urea, phosgene, or carbon dioxide, and subjecting it to a ring closure reaction.

An example will be explained. For example, 1,3-
In the case of dibutyl-4-methyl-2-imidazolidinone,
First, 1,2-dichloropropane and n-butylamine are reacted to obtain N, N'-dibutyl-1,2-diaminopropane. In the reaction of 1,2-dichloropropane and n-butylamine, a higher molar ratio of n-butylamine is preferable, and a low molar ratio of n-butylamine tends to increase by-products.

The temperature of the amination reaction is not limited as long as it is within a range that gives an appropriate reaction rate, but preferably 80 to 15
It is 0 ° C. The reaction pressure needs to be increased according to the reaction temperature.

Next, this N, N'-dibutyl-1,2-diaminopropane is reacted with urea. Reaction temperature is 100
It is preferably selected in the range of ˜155 ° C., and when the reaction temperature is higher than 155 ° C., urea is decomposed, which is not preferable.

The molar ratio of N, N'-dibutyl-1,2-diaminopropane to urea is preferably such that urea is provided in a stoichiometric ratio or more, but excessive use of urea is economically disadvantageous.

As the reaction solvent, ethanol, methyl isobutyl ketone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone or the like can be used.

When a solvent having a high boiling point is used as the reaction pressure,
The reaction can be carried out at normal pressure, but when using a solvent having a low boiling point, it is necessary to pressurize.

After sufficiently reacting the reaction solution of N, N'-dibutyl-1,2-diaminopropane and urea, the reaction temperature is kept at 190 to 250 ° C. for ring closure reaction to obtain the desired product 1,3 -Dibutyl-4-methyl-2-imidazolidinone is produced. The produced 1,3-dibutyl-4-methyl-2-imidazolidinone is separated and purified from the reaction solution by a general separation and purification method such as distillation.

[0016]

The present invention will be described in more detail with reference to the following examples and reference examples. Example 1 A 1 l pressure reactor equipped with a thermometer and a stirrer
2-dichloropropane 67.8 g (0.6 mol), n-
526.6 g (7.2 mol) of butylamine was charged, the temperature in the reactor was raised to 120 ° C. with stirring, and the amination reaction was continued for 12 hours while maintaining 120 ° C. to 130 ° C. Then, the reaction solution was cooled to room temperature and analyzed by gas chromatography to find that the conversion rate of 1,2-dichloropropane was 100.0%. Next, after 240.0 g of a 20.0% aqueous sodium hydroxide solution was charged and neutralized, residual normal butylamine was recovered by distillation. The residual liquid after distillation forms two layers.
The N'-dibutyl-1,2-diaminopropane layer and the aqueous layer containing sodium chloride were separated. This N, N'-dibutyl-1,
2-diaminopropane and urea 28.6 g, 1,3-dimethyl-2-imidazolidinone 66.7 g reflux condenser,
The mixture was placed in a 0.3 l flask equipped with a thermometer and a stirrer, and the reaction was continued for 4 hours while maintaining the temperature in the reactor at 130 to 135 ° C with stirring, and then 220 to 225 ° C.
The ring-closing reaction was carried out for 4 hours. After that, the reaction solution is distilled (1
By heating at 53 ° C./7 mmHg), 100.4 g of 1,3-dibutyl-4-methyl-2-imidazolidinone having a purity of 99.6% was obtained. The yield of this product on the basis of 1,2-dichloropropane was 78.3%. ¹ HN in Figure 1
An MR chart and IR spectrum are shown in FIG.

Example 2 An amination reaction and a ring closure reaction were tried under the same conditions as in Example 1 except that n-butylamine was replaced by n-propylamine.
As a result, boiling points 261-262 ° C (128 ° C / 6 mmH
9-3% pure 1,3-dipropyl-4 having g)
-Methyl-2-imidazolidinone was obtained. The yield of this product based on 1,2-dichloropropane was 77.0%. FIG. 2 shows the ¹ H NMR chart and FIG. 4 shows the IR spectrum.

Reference Example 1 In a 0.5 l reactor equipped with a stirrer and a thermometer, 157.6 g of para-nitrochlorbenzene, 96.
7 g and 100.0 g of 1,3-dibutyl-4-methyl-2-imidazolidinone obtained in the example as a reaction solvent
Was charged, 52.0 g of sodium hydroxide was charged in 10 portions at 0.5 hour intervals, and after charging, reaction was carried out at 60 ° C. for 5 hours to synthesize para-nitrophenetol. Then, 225.4 g of a 3.7% hydrochloric acid aqueous solution was added to neutralize. Separate the neutralized reaction solution into an oil layer containing para-nitrophenetol and 1,3-dibutyl-4-methyl-2-imidazolidinone and an aqueous layer containing salt, and easily remove water and salt from the reaction solution. Was possible. The results of quantitative analysis of the oil layer by high performance liquid chromatography are shown in Table 1.

Reference Example 2 The reaction solvent was 1,3-dibutyl-4-methyl-2-imidazolidinone to 1,3-dipropyl-4-methyl-2-.
The reaction and operation were carried out under the same conditions as in Reference Example 1 except that imidazolidinone was used instead. As a result, the reaction solution after neutralization was separated into an oil layer and an aqueous layer as described above, and it was possible to easily remove water and salt from the reaction solution as described above. The results of quantitative analysis of this oil layer by high performance liquid chromatography are shown in Table 1.

Reference Example 3 Paranitrophene as in Reference Example 1 except that the reaction solvent was changed from 1,3-dibutyl-4-methyl-2-imidazolidinone to 1,3-dimethyl-2-imidazolidinone. The process was carried out until Toll synthesis. Next, add 36% hydrochloric acid aqueous solution to 31.9
g was added for neutralization. As a result, the reaction liquid after neutralization was in a slurry state, and the liquid separation state as in Reference Examples 1 and 2 was not observed. After that, water was distilled off and filtration was performed, so that water and salt could be finally removed from the slurry reaction solution. This reaction solution was quantitatively analyzed by high performance liquid chromatography, and the results are shown in Table 1.

[0021]

[Table 1]

In the above table, para-nitrochlorbenzene is abbreviated as PNCB and para-nitrophenetol is abbreviated as PNPT, and% is based on weight.

[0023]

As shown in Reference Example, when the present invention is used as a reaction solvent, the reaction results are comparable to those of 1,3-dimethyl-2-imidazolidinone. Further, unlike 1,3-dimethyl-2-imidazolidinone, it plays a role as an extraction solvent, and the target substance can be easily taken out by a liquid separation operation. The effect of the present invention is also significant from such effects.

[Brief description of drawings]

FIG. 1 shows a ¹ HNMR chart of 1,3-dibutyl-4-methyl-2-imidazolidinone.

FIG. 2 shows an IR spectrum of 1,3-dibutyl-4-methyl-2-imidazolidinone.

FIG. 3 shows a ¹ HNMR chart of 1,3-dipropyl-4-methyl-2-imidazolidinone.

FIG. 4 shows an IR spectrum of 1,3-dipropyl-4-methyl-2-imidazolidinone.

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[Procedure amendment]

[Submission date] February 14, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 shows a ¹ HNMR chart of 1,3-dibutyl-4-methyl-2-imidazolidinone.

FIG. 2 shows a ¹ H NMR chart of 1,3-dipropyl-4-methyl-2-imidazolidinone.

FIG. 3 shows an IR spectrum of 1,3-dibutyl-4-methyl-2-imidazolidinone.

FIG. 4 shows an IR spectrum of 1,3-dipropyl-4-methyl-2-imidazolidinone.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Teruyuki Nagata 30 Asmuta-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A compound represented by the general formula (1): [In the formula, R represents a propyl group or a butyl group. ] 1,3-Dialkyl-4-methyl-2-imidazolidinone represented by