JP3184745B2 - Bisurea compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel bisurea compound and a method for producing the same. Specifically, 1,3
A novel bisurea compound useful for producing -dialkyl-2-imidazolidinones and a method for producing the same.

[0002]

2. Description of the Related Art Equation (2)

Embedded image [Wherein, R represents an alkyl group. The 1,3-dialkyl-2-imidazolidinones represented by the formula (1) are useful as intermediates in aprotic polar solvents, pharmaceuticals and agricultural chemicals. It is an excellent solvent especially for high molecular compounds such as polyamides, polyvinyl chloride, polyvinyl alcohol, polystyrene, polyurethane, and phenolic resin. Can be

[0003] Several methods for producing 1,3-dialkyl-2-imidazolidinones have been proposed. For example, for 1,3-dimethyl-2-imidazolidinone, ethylenediamine is reacted with urea to obtain 2-imidazolidinone, and the reaction product obtained by adding formaldehyde thereto is reduced with trichloroacetic acid, formic acid, or the like. N, N '
-A method of dimethylation, and a method of hydrogenolysis under acidic conditions using a noble metal catalyst by improving this reduction method, and a method of decomposing N, N'-dimethylethylenediamine into phosgene and / or trichloroformate into phosgene. A method of causing a reaction is known.

Further, N, N'-dialkylethylenediamines are reacted with urea to give 1,3-dialkyl-
The present inventors have previously proposed an industrial process for obtaining 2-imidazolidinones (USP 4,731,453).
However, when N, N'-dialkylethylenediamines as raw materials are produced from dichloroethane and alkylamine, N, N ', N "-trialkyldiethylenetriamines as by-products are formed. The yields of 1,3-dialkyl-2-imidazolidinones were 68% in the case of 1,3-dimethyl-2-imidazolidinone, 70% in the case of 1,3-diethyl-2-imidazolidinone, and 1%. , 3-dipropyl-2
In the case of -imidazolidinone, 82%, and in the case of 1,3-dibutyl-2-imidazolidinone, 85%, which are not industrially satisfactory. The by-products N, N ',
The main use of N "-trialkyldiethylenetriamines has not been developed, and the development of useful applications thereof has been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an intermediate which is useful for producing 1,3-dialkyl-2-imidazolidinones and a method for producing the intermediate. Furthermore, the present invention relates to 1,3-dialkyl-2-
N, N ', by-produced during the production of imidazolidinones
It is another object of the present invention to provide a method for effectively utilizing N "-trialkyldiethylenetriamines.

[0006]

In order to achieve the above object, the present inventors have studied to create a starting compound useful for the synthesis of 1,3-dialkyl-2-imidazolidinones.
Bisurea compounds that can be synthesized from N ′, N ″ -trialkyldiethylenetriamines as raw materials and a method for producing the same have been found.

That is, the present invention provides: Equation (3)

Embedded image [Wherein, R represents an alkyl group. A bisurea compound represented by

[0008] 2. Equation (1)

Embedded image [Wherein, R represents an alkyl group. N,
A method for producing a bisurea compound represented by the formula (3), comprising reacting urea with N ′, N ″ -trialkyldiethylenetriamine.

According to the present invention, it is possible to effectively use N, N ', N "-trialkyldiethylenetriamine, which has no main use and whose development is desired,
The significance of the present invention is great.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION N, N ',
The N ″ -trialkyldiethylenetriamines are represented by the above formula (1). Using this as a raw material, a bisurea compound represented by the formula (3) is obtained. 1,3-dialkyl-2-imidazolidinone represented by the following formula:

In equations (1), (2) and (3),
R represents an alkyl group. Preferably it is a C1-C8 alkyl group, More preferably, it is a C1-C4 alkyl group. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-butyl
-Pentyl group, t-pentyl group, n-hexyl group, i-
Examples include a hexyl group, an n-octyl group, a 2-ethylhexyl group, and the like.

The N, N ',
The N ″ -trialkyldiethylenetriamines are preferably prepared by reacting with the reaction formula (A)

Embedded image Can be produced by the reaction shown in the above. If necessary, it can also be produced by reacting N, N'-dialkylethylenediamine with dichloroethane in the presence of an alkylamine.

In a preferred production of N, N ', N "-trialkyldiethylenetriamines as raw materials,
The molar ratio of 1,2-dichloroethane to alkylamine is preferably 4 to 6 times that of 1,2-dichloroethane, and the higher the molar ratio of alkylamine, the lower the yield of N, N'-dialkylethylenediamine. It tends to increase.

The temperature of the amination reaction is not limited as long as it is within a range that gives an appropriate reaction rate, but is preferably 80 to 1
50 ° C. The reaction pressure of the amination reaction needs to be increased according to the reaction temperature.

The produced N, N ', N "-trialkyldiethylenetriamines are subjected to neutralization of the aminated reaction mass with a suitable base such as caustic soda, and then unreacted alkylamine is distilled off and recovered. The N, N ', N "-trialkyldiethylenetriamines thus obtained can be used in the production method of the present invention.

The compound of the present invention represented by the formula (3) can be produced by reacting the compound of the formula (1) with urea.

The reaction temperature is preferably 100 to 155 ° C.,
More preferably, it is 120 to 145 ° C. When the reaction temperature is higher than 155 ° C., urea is decomposed, and when the reaction temperature is lower than 100 ° C., the reaction rate tends to decrease. N,
The amount of N ', N "-trialkyldiethylenetriamines and urea used is preferably 1.5 to 2.5 urea relative to N, N', N" -trialkyldiethylenetriamines.
The molar ratio is adjusted. If too much urea is used, solid impurities such as cyanuric acid, which is a thermal decomposition product of urea, remain in the reaction system, and if the molar ratio is less than 1.5, the amount of by-products increases.
This reaction proceeds quantitatively, and the end point can be determined by quantifying the amount of ammonia gas released together with the reaction.

The compound of the formula (2) can be produced by thermally decomposing the compound of the formula (3). The temperature in this decomposition reaction is preferably 180 ° C. or higher, more preferably 2 ° C.
The temperature is from 00 to 260 ° C, most preferably from 210 to 240 ° C. If the reaction temperature is lower than 180 ° C., the reaction rate tends to decrease. At about 300 ° C., there is a problem in the heating method.

The compound (2) can also be produced by reacting the compound (1) with urea and thermally decomposing the obtained bisurea compound without separating the obtained compound (3). A series of reactions for producing a compound (3) from a compound (1) via a compound (2) is shown in a reaction formula (B).

Reaction formula (B)

Embedded image In this reaction, the reaction is carried out stepwise at the reaction temperature and conditions of the above-mentioned method for producing compounds (3) and (2).

A method for producing compound (3) from compound (1), a method for producing compound (2) from compound (3),
And in any method for producing compound (2) without removing compound (3) from compound (1), ethanol, methyl isobutyl ketone, N-
Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like can be used. However, in the method of the present invention, from the viewpoint of avoiding the complexity of steps such as solvent evaporation, etc. It is desirable to carry out the reaction without solvent. The produced 1,3-dialkyl-2-imidazolidinones are purified by distillation.

[0022]

The present invention will be described in more detail with reference to the following examples.

Production Example 1 [Synthesis of Compound (1)] 1286.5 g (13 mol) of 1,2-dichloroethane and 2018.9 g of methylamine were placed in a 5.0-liter pressure reactor equipped with a thermometer and a stirrer. (65 mol), the temperature was raised to 100 ° C. while stirring the inside of the reactor, and the amination reaction was continued for 2 hours while maintaining the temperature. Then, the reaction solution was cooled to room temperature, and analyzed by gas chromatography. As a result, the conversion of 1,2-dichloroethane was 100.0%. Then add 10 pieces of flake caustic soda
After charging 72.2 g and neutralizing, the remaining methylamine was recovered by distillation. This methylamine can be reused. The sodium chloride deposited on the reaction mass after the distillation was filtered off, and the filtrate was distilled to obtain 229.4 g of N, N ′, N ″ -trimethyldiethylenetriamine.

Example 1 [Synthesis of Compound (3)] 171.3 g (1.0 mol) of N, N ', N "-trimethyldiethylenetriamine obtained in Production Example 1 and urea 12
0.1 g (2.0 mol) was charged into a 0.5-liter flask equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised while stirring the inside of the reactor.
The reaction was carried out for 3 hours while maintaining the temperature at 0 ° C. Thereafter, upon cooling, the reaction mass solidified at around 90 ° C. The solidified reaction mass was pulverized and dissolved in ethanol at 60 ° C., and crystallized, filtered, washed and dried using hexane to obtain 186.1 g (yield: 80.2%) of a bisurea compound. The melting point of this bisurea compound was 145 to 147 ° C., and its structure was confirmed by 1 H NMR, 13 C NMR, IR, and FAB-MS (NH ⁺ / Z = 232). The analysis results of 1H NMR, 13C NMR and IR are shown below. 1H NMR; (DMSO-d6, ppm) δ = 2.2 (s, 3H), 2.4 (t, 4H), 2.8
(S, 6H), 3.2 (t, 4H), 5.8 (s, b
(DMSO-d6, ppm) δ = 34 (q), 42 (q), 46 (t), 55
(T), 159 (s) IR; (KBr tablet) 1657 cm ^-1 (C = O)

Production Example 2 [Compound (3) to compound (2)
Synthesis of bisurea compound obtained in Example 1 115.7 g
(0.5 mol) was charged into a 0.5-liter flask equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was increased while stirring the inside of the reactor, whereby the bisurea compound began to melt from around 145 ° C. It became completely liquid at 160 ° C. The temperature was raised as it was, and stirring was continued at 215 to 225 ° C for 4 hours. After cooling and analysis by gas chromatography, the reaction yield of 1,3-dialkyl-2-imidazolidinone was 87.5%.

Production Example 3 [Synthesis of Compound (2)] 217.9 g (1.5 mol) of N, N ', N "-trimethylethylenetriamine obtained in Production Example 1 and 180.2 g of urea
g (3.0 mol) was charged into a 0.5-liter flask equipped with a reflux condenser, a thermometer and a stirrer, and reacted for 4 hours while maintaining the reactor at 125 to 140 ° C. while stirring. After that, the temperature was raised to 215 to 225 ° C., and the decomposition reaction of the bisurea compound was performed at the same temperature for 4 hours. After completion of the reaction, 1,3-dimethyl-2-imidazolidinone was quantified by gas chromatography to find N, N ′,
The yield based on N "-trimethyldiethylenetriamine was 88.0%.
Purity having a boiling point of 105 ° C. under a reduced pressure of 5 mmHg.
3% of 1,3-dimethyl-2-imidazolidinone is 13%
7.0 g were obtained.

Production Example 4 [Synthesis of compound (2)] Analysis was carried out. As a result, the yield of 1,3-diethyl-2-imidazolidinone based on N, N ′, N ″ -triethyldiethylenetriamine was 85.4%. The reaction solution was distilled under reduced pressure of 15 mmHg. 163.5 g of 1,3-diethyl-2-imidazolidinone having a boiling point of 109 ° C. and a purity of 99.4% were obtained.

Production Example 5 [Synthesis of Compound (2)] A reaction was conducted in the same manner as in Production Example 3 except that N, N ', N "-tripropyldiethylenetriamine was used instead of N, N', N" -trimethyldiethylenetriamine. ,Analysis was carried out. As a result, the production rate of 1,3-dipropyl-2-imidazolidinone was 81.2%. The reaction solution was distilled to obtain 134.6 g of 1,3-dipropyl-2-imidazolidinone having a boiling point of 110 ° C. and a purity of 99.6% under a reduced pressure of 5 mmHg.

Production Example 6 [Synthesis of Compound (2)] The reaction was carried out in the same manner as in Production Example 3 except that N, N ', N "-tributyldiethylenetriamine was used instead of N, N', N" -trimethyldiethylenetriamine. Analysis was carried out. As a result, the yield of 1,3-dibutyl-2-imidazolidinone based on N, N ', N "-tributyldiethylenetriamine was 80.3%. The reaction mixture was distilled under reduced pressure of 10 mmHg. 210.1 g of 1,3-dibutyl-2-imidazolidinone having a boiling point of 127 ° C. and a purity of 99.6% were obtained.

[0030]

The present invention provides a novel bisurea compound and a method for producing the same. This gives 1,3
A novel method for producing -dialkyl-2-imidazolidinone can be provided, and the effective use of N, N ', N "-trialkyldiethylenetriamine, which has no main use and has been desired to be developed for such use, has been desired. It becomes possible.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-119087 (JP, A) JP-B-44-934 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 275/14 C07D 273/18 C07D 233/32 CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] (1) Formula (3) [Wherein, R represents an alkyl group. A bisurea compound represented by the formula: 2. The compound according to claim 1, wherein R in the formula (3) is an alkyl group having 1 to 8 carbon atoms. 3. The compound according to claim 1, wherein in the formula (3), R is a methyl group. 4. Formula (1) [Wherein, R represents an alkyl group. N,
Formula (3) comprising reacting urea with N ′, N ″ -trialkyldiethylenetriamines. [Wherein, R represents an alkyl group. ] The method for producing the compound represented by the formula: 5. The method according to claim 4, wherein the reaction temperature is 100 to 155 ° C. 6. The method according to claim 4, wherein the reaction is carried out without a solvent. 7. The method according to claim 4, wherein in the formulas (1) and (3), R is an alkyl group having 1 to 8 carbon atoms. 8. The method according to claim 4, wherein in the formulas (1) and (3), R is a methyl group.