JP2000297077A - Production of triazinediamine crystal having high melting point - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a triazinediamine crystal having high melting point and enabling easy handling in industrial use by heating a specific compound composed of crystal of low melting point or a mixture of low-melting point crystal and high-melting point crystal at a specific temperature. SOLUTION: A crystal having high melting point can be produced by heating (RS)-N-[2-(3,5-dimethylphenoxy)-1-methylethyl]-6-(1-fluoro-1-methyleth yl)-1,3,5- triazine-2,4-diamine at >=60 deg.C and below the melting temperature (103-104 deg.C) of the low-melting point crystal, preferably >=70 deg.C and below the melting temperature of the low-melting point crystal. The heating can be carried out e.g. by contacting with a hot inert gas, contacting with a high-temperature solid or suspending in a scarcely dissolving solvent, etc. The heating time depends upon the heating temperature and a high-melting point crystal can be produced by heating for >=100 hr in the case of heating at 70 deg.C or for ten-odd hr in the case of heating at 80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION (RS) -N- [2- (3,5)
-Dimethylphenoxy) -1-methylethyl] -6- (1
The present invention relates to a method for producing a high melting point type crystal of (-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine (hereinafter referred to as β-type crystal) and a β-type crystal to be produced.

[0002]

2. Description of the Related Art (RS) -N- [2- (3,5-dimethylphenoxy) -1 which is used as an active ingredient in herbicides.
-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine includes low melting point type crystals (hereinafter referred to as α type crystals) and β type crystals 2
There are seed crystal forms.

[0003]

There is a demand for a β-type crystal which is industrially easy to handle and a method for producing the β-type crystal.

[0004]

According to the present invention, there is provided an (RS) -N- [2-] comprising an α-type crystal or an α-type crystal and a β-type crystal.
(3,5-dimethylphenoxy) -1-methylethyl] -6
A β-form crystal characterized by heating-(1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine in a range from 60 ° C. to a temperature lower than the melting temperature of the α-form crystal. It is a manufacturing method, and (beta) type crystal manufactured by the manufacturing method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Heating is performed by contact with a high-temperature inert gas (hereinafter, gas-solid heating method), contact with a high-temperature solid (hereinafter, solid heating method), or suspension with a sparingly soluble solvent (hereinafter, suspension). Turbidity heating method).

[0006] As the gas-solid heating method, a device having a gas-solid contact function such as a flash dryer, a fluid dryer, a through-air dryer, a hot-air dryer, or the like is provided with (RS) -N- [2- (3,5-). Dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-
There is a method in which 1-methylethyl) -1,3,5-triazine-2,4-diamine is charged, and a high-temperature gas such as heated air or heated nitrogen is blown into the mixture to perform a heat treatment.

[0007] The solid heating method includes a kneader with a jacket, a stirring dryer, a screw conveyor with a jacket,
(RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1) which is equipped with a heating equipment such as a conical dryer and has a mixing function. -Methylethyl) -1,3,5-triazine-
There is a method in which 2,4-diamine is charged and mixed by heating for a predetermined time.

[0008] As the suspension heating method, (RS) -N- [2- (3,
5-Dimethylphenoxy) -1-methylethyl] -6-
There is a method in which (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine is charged and heated while being suspended.

The heating temperature can be generally from 60 ° C. to less than the melting temperature of α-type crystal (melting point of α-type crystal: 103 to 104 ° C.), preferably from 70 ° C. to less than the melting temperature of α-type crystal.

[0010] The heating time usually depends on the heating temperature, and requires time until the α-form crystal substantially disappears. For example, 7
The β-type crystal can be formed in 100 hours or more when heating at 0 ° C., and over 10 hours when heating at 80 ° C.

By heating, the α-form crystal is transformed into the β-form crystal, then cooled, and further filtered by the suspension heating method to obtain the β-form crystal.

In the gas-solid heating method and the solid heating method, the β-form crystal can be obtained as a solid, and can be used as it is or after being pulverized, for example, for producing an aqueous suspension pesticide composition.

[0013] In the gas-solid heating method and the solid heating method, an α-type crystal mainly produced by a crystallization method (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
The use of -1,3,5-triazine-2,4-diamine allows the β-form crystals to be formed as a powder without being formed into a solid mass in the above-mentioned apparatus, so that high productivity can be maintained. At that time, (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1) mainly consisting of α-form crystals substantially containing no crystallization solvent.
-Methylethyl) -1,3,5-triazine-2,4-diamine is preferred.

In the suspension heating method, it may be necessary to remove the hardly soluble solvent. For example, when the poorly soluble solvent is water, a drying step may be required. However, when obtaining an aqueous suspension pesticide composition, drying is not necessary depending on the concentration of the suspension weight.

[0015] In the suspension heating method, in the heating operation,
Since the dispersion state in the device can be kept good, (RS) -N
-[2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,
The temperature of 5-triazine-2,4-diamine can be easily controlled, and a uniform β-type crystal can be efficiently produced. further,
The β-type crystals produced by the suspension heating method have excellent filterability and are easy to dry.

A method for obtaining a desired β-type crystal by suspending in water which is a poorly soluble solvent and is industrially inexpensive will be described below.

That is, (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-) comprising α-type crystals or α-type and β-type crystals in water. Fluoro-1-methylethyl) -1,3,5-triazine-2,
A solution in which 4-diamine is usually suspended in an amount of 0.1 to 60% by weight, preferably 1 to 60% by weight, is heated at a temperature of 70 ° C. or more to less than α-type crystal melting temperature for 10 minutes to 100 minutes.
Time, preferably from 80 ° C. to below the α-type crystal melting temperature.
The mixture is held for 0 to 40 hours, and then cooled to a temperature at which ordinary filtration can be performed, usually 50 ° C or lower, preferably 40 ° C or lower, and then filtered. When the crystals are completely transformed into β-form crystals, the drying can be performed at a temperature lower than the melting temperature of β-form crystals, usually lower than the melting temperature of α-form crystals, and preferably 75 ° C. or lower.

[0018]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
The weight ratio between the α-type crystal and the β-type crystal approximated the area ratio of each endothermic peak in differential scanning calorimetry, and was determined from each endothermic area ratio.

Example 1 (RS) -N- [2- (3,5-dimethylphenoxy) containing 0.2% by weight of β-type crystal in a kneader equipped with a 20L biaxial U-trough type jacket.
Α- of 1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine
20 kg of the type crystal was charged and mixed. The jacket was heated to 80 ° C. by passing warm water through it. 80 hours later, (RS) -N
-[2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,
Differential scanning calorimetry of 5-triazine-2,4-diamine was carried out, and it was confirmed that the entire amount was changed to β-form crystal.

Example 2 After heating at 75 ° C. for 100 hours according to Example 1, (RS) -N- [2- (3,5-
Dimethylphenoxy) -1-methylethyl] -6- (1-
Differential scanning calorimetry of (fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was carried out, and it was confirmed that the entire amount was changed to β-form crystal.

[Example 3] (RS) -N- [2-
(3,5-dimethylphenoxy) -1-methylethyl] -6
5 kg of α-form crystal of-(1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was charged,
Mixed. The jacket was heated to 90 ° C. by passing warm water through it. After 8 hours, (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2 , 4-
Differential scanning calorimetry of the diamine was carried out, and it was confirmed that the entire amount was changed to β-form crystal.

[Example 4] β was added to a 5 L conical dryer.
(RS) -N- containing 0.2% by weight of a type crystal
[2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,
1 kg of α-form crystal of 5-triazine-2,4-diamine
Charged and mixed. Hot water was passed through the jacket and heated to 65 ° C. Three months later, (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-
Differential scanning calorimetry of 2,4-diamine was carried out, and it was confirmed that the entire amount was changed to β-type crystal.

[Example 5] β was added to a 10 L conical flash dryer.
(RS) -N- containing 0.2% by weight of a type crystal
[2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,
3 kg of α-form crystal of 5-triazine-2,4-diamine
Charged, heated air was blown and heated to 90 ° C. After 8 hours, (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2 Differential scanning calorimetry of 1,4-diamine was carried out, and it was confirmed that the whole amount was changed to β-type crystal.

Example 6 After heating at 75 ° C. for 100 hours according to Example 5, (RS) -N- [2- (3,5-
Dimethylphenoxy) -1-methylethyl] -6- (1-
Differential scanning calorimetry of (fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was carried out, and it was confirmed that the entire amount was changed to β-form crystal.

[Example 7] (RS) -N- [2-
(3,5-dimethylphenoxy) -1-methylethyl] -6
1 kg of α-form crystal of-(1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was charged,
Heated air was blown in and heated to 90 ° C. Eight hours later,
(RS) -N- [2- (3,5-dimethylphenoxy) -1
-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was subjected to differential scanning calorimetry, and it was confirmed that the total amount had changed to β-type crystals. confirmed.

Example 8 A 2 L jacketed reaction flask contained 0.2% by weight of β-form crystals (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
60 g of α-form crystal of-1,3,5-triazine-2,4-diamine and 240 g of water were charged to prepare a 20% by weight suspension solution. Warm water was passed through the jacket and heated to 90 ° C. with stirring. After 4 hours, (RS) -N- [2- (3,5-dimethylphenoxy) -1 suspended in the solution
-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried, and subjected to differential scanning calorimetry. Was confirmed to have changed to a β-type crystal.

Then, the warm water in the jacket was drained, and the suspension was cooled. (RS) -N- [2- (3,5-dimethylphenoxy) suspended in the solution at room temperature after cooling
-1-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried at about 55 ° C., and subjected to differential scanning calorimetry. Conduct,
It was confirmed that the whole amount was maintained in the β-type crystal.

Example 9 A 2 L jacketed reaction flask contained 0.2% by weight of β-form crystals (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
120 g of α-form crystals of-1,3,5-triazine-2,4-diamine and 180 g of water were charged to prepare a 40% by weight suspension solution. Hot water was passed through the jacket and heated to 80 ° C. with stirring. After 40 hours, (RS) -N- [2- (3,5-dimethylphenoxy) -1 suspended in the solution
-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine A part of the sample was collected by filtration, dried at about 45 ° C., and then subjected to differential scanning calorimetry. Was carried out, and it was confirmed that the entire amount was changed to a β-type crystal.

Example 10 A 2 L jacketed reaction flask contained 10% by weight of β-form crystal (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
40 g of α-form crystals of-1,3,5-triazine-2,4-diamine and 240 g of water were charged to prepare a suspension solution of about 14% by weight. Warm water was passed through the jacket and heated to 90 ° C. with stirring. After 4 hours, (RS) -N- [2- (3,5-dimethylphenoxy) -1 suspended in the solution
-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried, and subjected to differential scanning calorimetry. Was confirmed to have changed to a β-type crystal.

Thereafter, the warm water in the jacket was withdrawn, and the suspension was cooled. (RS) -N- [2- (3,5-dimethylphenoxy) suspended in the solution at room temperature after cooling
-1-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried at about 50 ° C., and subjected to differential scanning calorimetry. Conduct,
It was confirmed that the whole amount was maintained in the β-type crystal.

Example 11 A 2 L jacketed reaction flask contained 10% by weight of β-form crystals (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
15 g of α-form crystals of-1,3,5-triazine-2,4-diamine and 240 g of water were charged to prepare a suspension solution of about 6% by weight. Hot water was passed through the jacket and heated to 85 ° C. with stirring. After 20 hours, (RS) -N- [2- (3,5-dimethylphenoxy) -1 suspended in the solution
-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried, and subjected to differential scanning calorimetry. Was confirmed to have changed to a β-type crystal.

Thereafter, the warm water in the jacket was withdrawn, and the suspension was cooled. (RS) -N- [2- (3,5-dimethylphenoxy) suspended in the solution at room temperature after cooling
-1-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried at about 55 ° C., and subjected to differential scanning calorimetry. Conduct,
It was confirmed that the whole amount was maintained in the β-type crystal.

[Embodiment 12] According to the embodiment 11, 80
After heating at 40 ° C for 40 hours, it is suspended in the solution (RS)-
N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,
A portion of 3,5-triazine-2,4-diamine was collected by filtration, dried, and subjected to differential scanning calorimetry to confirm that the entire amount had changed to β-type crystal.

Thereafter, the warm water in the jacket was extracted, and the suspension was cooled. (RS) -N- [2- (3,5-dimethylphenoxy) suspended in the solution at room temperature after cooling
[-1-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine is collected by filtration, dried at 60 ° C., and subjected to differential scanning calorimetry. Then, it was confirmed that the whole amount was maintained in the β-type crystal.

[Embodiment 13]
After heating at 70 ° C for 70 hours, it is suspended in the solution (RS)-
N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,
A part of the 3,5-triazine-2,4-diamine was collected by filtration, dried, and then subjected to differential scanning calorimetry to confirm that all of the 3,5-triazine-2,4-diamine had changed to β-type crystals.

Thereafter, warm water in the jacket was withdrawn, and the suspension was cooled. (RS) -N- [2- (3,5-dimethylphenoxy) suspended in the solution at room temperature after cooling
-1-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine was collected by filtration, dried at about 45 ° C., and subjected to differential scanning calorimetry. Conduct,
It was confirmed that the whole amount was maintained in the β-type crystal.

[Embodiment 14] According to the embodiment 11, 90
(RS) -N suspended in the solution after heating at 4 ° C for 4 hours.
-[2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,
After a part of 5-triazine-2,4-diamine was collected by filtration and dried, a differential scanning calorimetry was carried out, and it was confirmed that the whole amount was changed to β-form crystal.

Thereafter, the warm water in the jacket was withdrawn, and the suspension was cooled. (RS) -N- [2- (3,5-dimethylphenoxy) suspended in the solution at room temperature after cooling
[-1-Methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine is collected by filtration, dried at 60 ° C., and subjected to differential scanning calorimetry. Then, it was confirmed that the whole amount was maintained in the β-type crystal.

Example 15 A stirring vessel equipped with a 1000 L jacket contained 0.2% by weight of β-form crystal (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
25 kg of α-form crystal of 1,3,5-triazine-2,4-diamine and 475 kg of water were charged to prepare a 5% by weight suspension solution. Warm water was passed through the jacket and heated to 90 ° C. with stirring. After 8 hours, the suspension (R
S) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl)
After a part of-1,3,5-triazine-2,4-diamine was collected by filtration and dried, a differential scanning calorimetry was carried out, and it was confirmed that the whole amount was changed to β-form crystal.

Thereafter, the suspension was filtered with a 65 L centrifuge. Dry at 60 ° C. in a 600 L conical dryer under vacuum, and (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1-fluoro-1-methylethyl) ―1,3,5-triazine―
A dried product of β-crystal of 2,4-diamine was obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinji Kuwahara 6901-1, Onoda, Onoda-shi, Yamaguchi Nissan Chemical Industry Co., Ltd. Onoda Plant (72) Inventor Takahisa Muramoto 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (72) Inventor Hidehiro Matsunami 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (6)

[Claims] 1. (RS) -N- [2- (3,5-dimethylphenoxy) -1-methylethyl] -6- (1) comprising a low melting point type crystal or a low melting point type crystal and a high melting point type crystal. -Fluoro-1-methylethyl) -1,3,5-triazine-2,
A method for producing a high melting point type crystal, comprising heating a 4-diamine in a range from 60 ° C. to a temperature lower than the melting point of the low melting point type crystal. 2. The heating is carried out by contact with a high-temperature inert gas, contact with a high-temperature solid, or suspension with a sparingly soluble solvent.
Manufacturing method. 3. The method according to claim 1, wherein the heating is performed in a suspension with a hardly soluble solvent. 4. The method according to claim 3, wherein the hardly soluble solvent is water. 5. 1 to 60% by weight of (RS) -N- [2- (3,5-dimethylphenoxy) -1 based on water.
The method according to claim 4, wherein -methylethyl] -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine is suspended. 6. A high melting point type crystal produced by the production method according to claim 1.