JPS5839801B2 - Method for producing emulsion of thiolcarbamate ester compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the general formula (where R and R1 represent an alkyl group or an allyl group, and R and R1 can also form a heterocycle together with adjacent nitrogen atoms).

A represents a linear or branched alkylene group, X represents a halogen atom, a methyl group or a methoxy group, and Z represents an oxygen atom or a sulfur atom.

m represents O or 1, n represents O or an integer of 1 to 3,
When n is 2 or 3, X may be different.

) is a method for producing an emulsion characterized by adding resorcinol, catechol, hydroquinone, or pyrogallol to a Nisder thiol carbamate compound represented by The object of the present invention is to obtain an emulsion of a thiol carbamate ester compound that is stable over time and does not undergo physical changes such as crystal precipitation during winter.

The thiol carbamate ester compounds represented by the above general formula have efficacy as herbicides, insecticides, or fungicides, and some of them in particular are widely used at home and abroad.

These thiol carbamate ester compounds can be dissolved in a solvent such as acetone or methanol, or a low concentration hydrating agent 1. If it is formulated into an emulsion and subjected to biological tests such as herbicidal, insecticidal, and sterilization, its potency can be confirmed, but when it is formulated into a commercially available pesticide form, that is, a highly concentrated emulsion, its physicochemical properties There are some problems.

Forms of use of agricultural chemicals include spraying the formulation as it is, granules and powders with a relatively low concentration of the active ingredient, emulsions and irrigation agents that are formulated at a high concentration and diluted with water before use.
There are sol preparations, etc., and in powders and granules with relatively low concentrations of the active ingredient, the influence of the physicochemical properties of the active ingredient is small, but as the concentration increases, formulation becomes difficult due to the properties of the active ingredient, and there is a limit naturally. arise.

However, it is more economical to use these products diluted with water to make them as highly concentrated as possible.

That is, the concentration of the active ingredient should be as high as possible, and the filler,
Reducing the amount of adjuvants other than the active ingredient, such as surfactants, and increasing the dilution ratio during use will lead to reductions in processing costs, shipping costs, and storage fees per certain amount of active ingredient.

Emulsions can be made by simply dissolving the active ingredient in a solvent, surfactant, etc. to form a homogeneous liquid, and because of its fluidity, transportation and packaging during the manufacturing process can be easily mechanized, increasing productivity.

On the other hand, with water conservancy agents, the active ingredients are pulverized or adsorbed together with adjuvants and mixed with a solid bulking agent, so the cost is high due to pulverization, and since they are powders, transportation and packaging during the manufacturing process are difficult. Easy to cause mechanical trouble.

Therefore, in determining the formulation of the same active ingredient, emulsion is more advantageous from a physicochemical standpoint.

Generally, liquid active ingredients have good solubility in solvents and are easy to form into emulsions, but emulsions containing crystalline active ingredients solidify as temperatures drop in winter and soften as temperatures rise from spring to summer. - Because the physical properties of emulsions repeatedly change due to changes in temperature throughout the year, especially in highly concentrated emulsions, crystals precipitate in the winter, causing damage to the container and non-uniformity of the components in the drug product.

The term "crystalline active ingredient" as used herein refers to one with a melting point of -5°C or higher.

When formulating these active ingredients whose state is easily changed by changes in temperature, technical consideration must be given to selecting additives and solvents that can withstand changes in temperature.

That is, it is necessary to take measures such as providing a sufficient margin for solubility or using a solvent with high solubility.

Formulation can be made easier by adding a melting point depressant to a solid substance to liquefy it, or by lowering the melting point without liquefying it so that it is less likely to solidify even when the temperature drops.

It is well known that a mixture of two compounds exhibiting a eutectic phenomenon will exhibit the lowest melting point at a certain ratio, but there is no example of this being done for thiol carbamate ester compounds.

According to the description in Japanese Patent Publication No. 441307, hydroxyl group 1
Phenols with one hydroxyl group are used as melting point depressants in carbamate insecticides, but as low-temperature stabilizers for emulsions of thiol carbamate compounds, phenols with one hydroxyl group are less effective and are not practical. It does not show any possible effects.

Furthermore, since the amount of phenols added is large, there is a possibility that the physicochemical properties of phenols and adverse effects on living organisms, such as a unique irritating odor and associated health and safety and pollution problems, may occur. It is not desirable in terms of toxicity and irritation.

The present inventors investigated various additives in order to research a method for producing physically stable high-concentration emulsions of crystalline thiol carbamate ester compounds. It was discovered that adding a small amount of hydroquinone or pyrogallol brings about a remarkable effect, and based on this knowledge, the present invention was completed.

According to the present invention, the amount added is as small as 1 to 5 of the active ingredients, and it can be used with confidence without any harmful effects on humans or animals or on plants (phytotoxicity). It is much cheaper than using expensive solvents with good properties or adding other crystallization inhibitors (such as melting point depressants).

Furthermore, the addition timing may be such that the solvent, surfactant, dispersant, etc. are added to the main ingredient at the same time as they are uniformly mixed and dissolved, and there is an advantage that no pre-treatment is required.

The emulsion of the present invention is free from crystal precipitation even at extremely low temperatures of 110° C. or lower.

Examples of the solvent used in the emulsion of the present invention include aromatic solvents such as quidylol, doluol, penzole, and alkylnaphthalene, and those commonly used in emulsions of agricultural chemicals, such as alcohol and ketone.

Examples of surfactants include anionic and nonionic surfactants commonly used in agricultural chemicals, such as alkyl allyl sulfonates, polyoxyalkylene alkyl allyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan alkylates, and polyoxyalkylene fatty acids. Single and mixed products such as esters and polyoxyalkylene alkyl ethers are mentioned.

Examples of the thiol carbamate ester compounds used in the present invention include the following.

m, p. indicates the melting point.

Compound I N,N-dimethyl S-phenyloxybutyl Thiol carbamate compound 2 N,N-diisopropyl S Thiol carbamate benzyl compound 3 N,N-dimethyl 5-(4-brome) Benzylthiol carbamate compound 4 N,N-dimethyl 5 -(2,5-dimethyl)benzylthiol carbamate compound 5 N,N-dimethyl 5-(2-chloro-5-
methoxy)benzyl thiol carbamate compound 6 N,N-dimethyl 5-(3,4-dichloro)benzylthiol carbamate compound 7 N,N-diethyl 5-(4-chlor) benzylthiol carbamate compound 8 N,N-hexamethylene α .

α-Dimethylbenzylthiol carbamate compound 9 N,N-pentamethylene α,α-dimethylbenzylthiol carbamate compound 1O N,N diethyl S (2 chlor) Benzylthiol carbamate compound 1 N,N-diisopropyl 5-(2 chlor)benzyl Thiol carbamate compound 1 N,N dimethyl S Penzylthiol carbamate compound 1 N,N-dimethyl S-3-(2-methylphenoxy)propyl Thiol carbamate compound 1 N,N-dimethyl S-2-(3-methylphenoxy) Ethyl thiol carbamate compound 1 N,N-dimethyl S-2-(4-chlorophenylthio)furovir Thiol carbamate compound 16 N,N-dimethyl S-phenylthiopropylthiol carbamate compound 17 N,N-dipropyl S Phenylthioethylthiol carbamate Compound 1 N,N-diallyl 5-(4-methoxy)benzylthiol carbamate compound l N,N-di-n-butyl S-(chloro4-methyl)benzylyl-benzylthiol carbamate compound 2O N,N-diethyl 5-(2-methoxy5-methyl)benzyl thiolcarbamate compound 21 N,N-dimethyl 5-(2,4,6-trimethyl)benzyl thiolcarbamate compound 22 N,N-diisopropyl S -(2,3゜4-Trichlor)benzyl thiol carpamate compound 23 N,N-diallyl 5-(2-chloro4-methyl)benzyl thiol carnocoumate compound 24 N,N-pentamethylene 5-(3-chloro4-methoxy)benzyl thiol Carbamate Examples and effects of the present invention are shown below, but the scope of the invention is not limited by these examples. It can also be applied to mixed preparations.

Example 1 137 parts of the compound, 3 parts of resorcin, 5 parts of Tsurpol (registered trademark: Toho Chemical Products), and 55 parts of Quijirole are uniformly mixed and dissolved to obtain an emulsion.

Example 2 740 parts of the compound, 2 parts of catechol, 7 parts of turpol, 51 parts of a mixed solvent of kijirole and triol are uniformly mixed and dissolved to prepare an emulsion.

Example 3 1250 parts of compound, 1 part of hydroquinone, 7 parts of Nucalgen (registered trademark name: Takemoto Oil Products), 42 parts of Kijirol
Mix and dissolve these parts uniformly to make an emulsion.

Example 4 845 parts of compound, 2 parts of pyrogallol, Nucal 776
1 part and 47 parts of Kijirole were uniformly mixed and dissolved to prepare an emulsion.

Example 5 42 parts of compound 1, 2 parts of catechol, 8 parts of turpol,
48 parts of Kijirole were uniformly mixed and dissolved to form an emulsion.

Example 6 736 parts of the compound, 2 parts of resorcinol, 6 parts of Tsurpol, and 56 parts of Kijirole were uniformly mixed and dissolved to prepare an emulsion.

Example 7 1252 parts of compound, 2 parts of catechol, 7 parts of turpol,
An emulsion was prepared by uniformly mixing and dissolving 39 parts of a mixed solvent of kijirole and doluol.

Example 8 Compound 1 51 parts, hydroquinone 1 part, Nucal 7
76 parts of pheasant and 42 parts of Kijirole were uniformly mixed and dissolved to form an emulsion.

Example 9 750 parts of the compound, 2 parts of hydroquinone, 7 parts of New Calgen, and 41 parts of Kijirole were uniformly mixed and dissolved to prepare an emulsion.

Example 10 1238 parts of compound, 2 parts of resorcinol, 6 parts of turpol,
54 parts of Kijirole were uniformly mixed and dissolved to form an emulsion.

Example 11 46 parts of Compound 1, 2 parts of pyrogallol, 7 parts of New Calgen, and 45 parts of quijirole were uniformly mixed and dissolved to prepare an emulsion.

Example 12 1248 parts of compound, 2 parts of pyrogallol, Nucal 77
6 parts and 44 parts of Kijirole were uniformly mixed and dissolved to form an emulsion.

Test Example 1 The emulsion was placed in a transparent glass bottle (capacity: 12 m1) with a diameter of 1 crrL and a height of 7 crrL, and left at -5°C for 72 and 120 hours, and the state of crystal precipitation at the bottom of the bottle was observed.

(According to the Ministry of Agriculture, Forestry and Fisheries Official Inspection Method (February 3, 1960 No. 71)).

The results are shown in Table 1.

Comparative Examples 1 to 12 are emulsions in which the additives resorcin, catechol, hydroquinone, and pyrogallol used in the corresponding actual cases 1 to 12, respectively, are excluded.

Further, Reference Examples 1 to 12 are the emulsions shown below.

Reference example 1 Example 1 except that resorcinol was replaced with 0-cresol.

Reference example 2 Example 2 except that catechol was replaced with xylenol.

Reference Example 3 Example 3 except that hydroquinone was replaced with p-cresol.

Reference example 4 Example 4 except that pyrogallol was replaced with phenol.

Reference example 5 Example 5 except that catechol was replaced with xylenol.

Reference example 6 Example 6 except that resorcinol was replaced with 0-cresol.

Reference example 7 Example 7 except that catechol was replaced with phenol.

Reference Example 8 Example 8 except that hydroquinone was replaced with p-cresol.

Reference example 9 Example 9 except that hydroquinone was replaced with phenol.

Reference example 10 The resorcinol of Example 10.

-Change to cresol.

Reference example 11 Example 11 except that pyrogallol was replaced with phenol.

Reference Example 12 Example 12 except that pyrogallol was replaced with xylenol.

From this test example, it is clear that by adding small amounts of resorcinol, catechol, hydroquinone, and pyrogallol, a highly concentrated emulsion of a thiol carbamate compound that is stable over time can be obtained.

Claims (1)

[Claims] General formula 1 (wherein R and R1 represent an alkyl group or an allyl group, and R and R1 can also form a heterocycle together with adjacent nitrogen atoms. A is a straight chain or branched represents an alkylene group, X represents a halogen atom, methyl group or methoxy group, Z represents an oxygen atom or a sulfur atom, m represents 0 or 1, n represents 0 or an integer from 1 to 3,
When n is 2 or 3, X may be different. 1. A method for producing an emulsion, which comprises adding resorcinol, catechol, hydroquinone or pyrogallol to a thiol carbamate ester compound represented by ().