JPS6310153B2 - - Google Patents

Description

[Detailed description of the invention]

In the production of fine particulate thiadiazine derivatives, the present invention provides fine particulate thiadiazine derivatives obtained by reacting dithiocarbamate and aldehyde in the presence of metal salts other than alkali metals, lanthanoid elements, and actinide elements and/or surfactants. The present invention relates to a method for producing thiadiazine derivatives. Among thiadiazine derivatives, 3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-thione (hereinafter referred to as DMTT) in particular decomposes in soil, producing methylamine, hydrogen sulfide, methylisothiocyanate, It is known to emit carbon disulfide and formalin, including hydrogen sulfide,
Carbon disulfide, methyl isothiocyanate, and formalin gases are said to contribute to the control of pathogenic bacteria, soil nematodes, and weeds, and are used as soil disinfectants and herbicides. In addition, this property makes it a useful compound that is widely used in disinfectants, slime control agents, preservatives, anti-bacterial agents, and the like. Conventionally, a simple reaction between a dithiocarbamate and an aldehyde has been known as a general method for producing thiadiazine derivatives. The above method can also be found in the literature for DMTT.
However, commercially available solid DMTT is mostly in powder form, and when used or handled, it becomes dust and scatters, causing problems such as irritation to the skin and mucous membranes of workers, which poses a hygiene problem. ing. In addition, in Patent Publication No. 57-57007, it is stated that the above-mentioned method is used to synthesize, then dried and pulverized as it is to obtain fine particles of 100 to 300 microns using a sieve machine, or after synthesizing DMTT,
Dry and grind to make a fine powder, use this fine powder to mix with additives, make fine particles by mechanical granulation methods such as extrusion type, rolling type, compression type, etc., and then sieve. Particles with a particle size range of 100 to 300μ have been obtained.
However, these methods require steps such as crushing, sieving, and granulation, making them complicated. Therefore, not only is the work complicated, but during these steps, DMTT becomes dust and scatters, causing harm to the health of the workers. Furthermore, these methods have drawbacks such as requiring special machinery and requiring large equipment costs. In view of these circumstances, the inventors of the present invention have conducted intensive studies on a method for producing granular thiadiazine derivatives that eliminates the above-mentioned drawbacks and is industrially advantageous.
We have discovered that it is possible to easily obtain fine granular products of a constant particle size with excellent fluidity, low disintegrability, and no dust generation at a low cost and with a good yield simply by a reaction process without the need for a special granulation process. , arrived at the present invention. That is, the present invention involves reacting a dithiocarbamate consisting of the primary amine with an aldehyde in an aqueous medium in the presence of a surfactant and/or the metal salt. This is a method for producing a finely divided thiadiazine derivative, which is characterized in that the thiadiazine derivative is finely divided during the reaction. According to the method of the present invention, the particle size can be easily controlled by changing the type of surfactant and stirring blade, and the desired fine particulate thiadiazine derivative with a diameter of 100 to 400 microns can be obtained in good yield. The feature of the present invention is a novel production method in which the thiadiazine derivative is made into fine particles during the reaction, and it is not yet known that the surfactant and/or the metal salt has the property of making the thiadiazine derivative into fine particles. This is a surprising fact. Since the surfactant and metal salt used here are added in very small amounts, they do not affect the purity of the thiadiazine derivative. In addition to the above-mentioned effects, the following effects can be obtained, and this is where the inventive step of the present invention lies. (1) Since a finely granular product is obtained during the reaction, the process is shortened by eliminating the need for a granulation process, and is economical as it saves expensive equipment, space, and manpower. (2) Because the process is shortened, handling losses are reduced and the overall yield is improved. (3) Since the product is in the form of fine particles, there is no need to worry about it solidifying into blocks, and the drying time is shortened, so there is no decrease in yield. Examples of surfactants that can be used in the present invention include alkyl sulfate salts, alkylbenzene sulfonate salts, alkyl naphthalene sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, and polyoxyethylene fatty acids. Examples include ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block polymer, and the like. Further, metal salts include metal salts excluding alkali metals, lanthanoid elements, and actinide elements, and specific examples include metal salts of zinc, aluminum, iron, nickel, barium, calcium, magnesium, cobalt, etc. Ru. If the salt of the anion is water-soluble,
It may be either an inorganic acid residue or an organic acid residue. Examples of primary amines include methylamine, propylamine, isopropylamine, benzylamine, cyclohexylamine, and aniline. The method of adding the surfactant is not particularly limited, and it may be added to the dithiocarbamate aqueous solution or to the aldehyde. There are no particular restrictions on the method of adding the metal salt, but it is preferable to add it to the aldehyde. The amount of surfactant added is usually
An amount in the range of 0.001% to 10% by weight is sufficient, and a sufficient effect is usually exhibited when the amount of metal salt used is in the range of 0.01% to 5% by weight based on the aldehyde. The reaction of the present invention involves adding a surfactant and/or a surfactant to an aldehyde.
Or, a primary amine and a metal salt added to the solution,
It is carried out by adding an amine salt of dithiocarbamic acid synthesized from carbon disulfide. In addition, a surfactant and/or a dithiocarbamic acid amine salt
Alternatively, an aldehyde solution containing a metal salt may be added. In this case, fluidity is inferior to the above method but superior to the conventional method. Furthermore, even when a surfactant and a metal salt are used alone without using them together, the fluidity is superior to the conventional method, but is inferior to the method using them together. By carrying out the present invention, fine-grained thiadiazine derivatives can be produced using only a simple reaction device, so the operation is easy, and since a granulation process is not required, there is no problem of dust during granulation, etc. It is industrially advantageous in this respect. Hereinafter, the effects of the present invention will be explained in detail using comparative examples and examples, but the present invention is not limited to the present examples. Comparative Example 1 After adding 34 g of 40 wt% methylamine aqueous solution and 60 ml of water to a four-necked flask equipped with a stirrer, 14.3 ml of carbon disulfide was added dropwise to synthesize methyldithiocarbamic acid methylamine salt, followed by 37 wt% formalin. Add 36g, filter, wash with water, dry and scatter.
DMTT powder was obtained. The melting point was 104-106°C, and the particle size distribution ratio was measured using a standard wire mesh film and was as follows.

[Table] Comparative Example 2 37wt% formalin 36 using the apparatus described in Comparative Example 1
An aqueous solution of methylamine salt of methyldithiocarbamate was added dropwise to the solution, followed by filtering, washing with water, and drying to obtain a scattering powder of DMTT. The results are shown in Table-1. Comparative Example 3 A reaction was carried out in the same manner as in Comparative Example 1, except that cyclohexylamine was used as the primary amine, to obtain a scattering powder. The results are shown in Table-1. Example 1 After adding 0.3 g of Emulgen PP-150 (manufactured by Kao Atlas), 0.3 g of zinc sulfate heptahydrate, and 30 ml of water to 36 g (0.44 mol) of 37wt% formalin, methylamine salt of methyldithiocarbamate (0.22 mol) was added. An aqueous solution of was added dropwise, filtered, washed with water, and dried to obtain DMTT in the form of fine particles with no scattering properties. The results are shown in Table-1. Example 2 A reaction was carried out in the same manner as in Example 1 except that formalin was added dropwise to the methyldithiocarbamic acid methylamine salt to obtain non-scattering fine DMTT.
The results are shown in Table-1. Example 3 The reaction was carried out in the same manner as in Example 1 except that 0.6 g of zinc sulfate heptahydrate was added, and fine particles with no scattering properties were obtained.
Got DMTT. The results are shown in Table-1. Examples 4 to 8 Reactions were carried out according to the method described in Example 1 while changing the metal salt and surfactant (manufactured by Kao Atlas) to obtain non-scattering, fine-grained DMTT. The results are shown in Table-1. Examples 9 to 12 The reaction was carried out in the same manner as in Example 1 except that the primary amine was changed to obtain non-scattering fine particulate tetrahydrothiadiazine-2-thione derivatives. The results are shown in Table-1. Example 13 Example 1 except that Emulgen PP-150 is not added.
The reaction is carried out in the same manner as in
Got DMTT. The results are shown in Table-1. Example 14 The reaction was carried out in the same manner as in Example 1 except that zinc sulfate heptahydrate was not added, and fine particles with no scattering properties were obtained.
Got DMTT. The results are shown in Table-1. Example 15 The reaction was carried out in the same manner as in Example 1 except that formalin was changed to benzaldehyde, and non-scattering fine particles of 3,5-dimethyl-4,6-diphenyl-
1,3,5-thiadiazine-2-thione was obtained.
The results are shown in Table-1.

【table】

[Table] (Note) Liquidity evaluation: ○Excellent △ Average × Poor

Claims (1)

[Claims] 1. In the presence of a metal salt and/or a surfactant,
A method for producing a finely divided thiadiazine derivative, which comprises reacting a dithiocarbamate with an aldehyde. 2. The method according to claim 1, wherein the primary amine forming the dithiocarbamate is methylamine, ethylamine, propylamine, isopropylamine, cyclohexylamine, benzylamine, or aniline. 3. The method according to claim 1, wherein the metal salt is a water-soluble salt excluding alkali metals, lanthanoid elements, and actinide elements. 4. The method according to claim 1, wherein the reaction solvent comprises water or a solvent substantially aqueous.