JPH039101B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel dithiocarbamate, a method for producing the same, and a pesticidal agent comprising the salt. BACKGROUND ART Alkylene bisdithiocarbamates, particularly alkali salts, ammonium salts, and heavy metal salts of ethylene bisdithiocarbamic acid and propylene bisdithiocarbamic acid, have been used as insecticides and fungicides. Since these have extremely high activity, research is also being carried out on derivatives using these as skeletons. Furthermore, many compounds are known in which various substituents have been introduced in place of hydrogen in the amino group of these salts. DE 2732331 describes zinc dithiocarbamates in which an alkyl group, in particular a tert-butyl group, has been introduced into one nitrogen atom, which shows that the formation of ethylenethiourea is extremely low and that the biological effect is It is stated that it has the same effect as Zineb. moreover,
According to Japanese Patent Publication No. 36-3849, a heavy metal salt of an N,N'-substituted compound in which two nitrogen atoms are substituted with hydroxyethyl groups is disclosed, and U.S. Pat.
No. 2733262 discloses water-soluble salts of N-substituted dithiocarbamic acids in which one nitrogen atom is substituted with a hydroxyethyl group, and in both cases it is described that they are used as agricultural chemicals. There is. In addition, Japanese Patent Application Laid-open No. 1989-55 by the same applicant
Publication No. 45632 describes a dithiocarbamate in which a substituent containing one carboxylic acid group or the like is introduced for one nitrogen atom. Thus, dithiocarbamate agents with functional groups are
When used as a pesticidal agent, favorable results have been obtained since it is believed that the metabolism in useful organisms is relatively fast. The present inventors provide a compound in which a substituent having a polycarboxylic acid or a functional derivative thereof is introduced to the nitrogen atom. These compounds are
It is effective as a pest killer in various fields, and its characteristics include having a broad antibacterial spectrum and easier manufacturing operations compared to conventional nitrogen-substituted dithiocarbamate agents.
One example is that it is industrially inexpensive.
Also, in terms of toxicity, it is far superior to dithiocarbamate agents that have been widely put into practical use. Furthermore, when used, it is also possible to treat it as a liquid preparation such as an emulsifier. In particular, since functional derivatives such as esters, amides, and nitriles are soluble in organic solvents, they have the advantage of eliminating the need for drying equipment and pulverization equipment in production equipment. Moreover, when used as a preparation, this property can be used as an emulsifier, so it can comply with the global trend of favoring the use of liquid preparations such as emulsifiers. As described above, the compound of the present invention can be easily handled in both manufacturing and usage aspects compared to conventional substituted dithiocarbamate agents, and has excellent industrial utility. Can be done. According to the invention, the general formula () [Wherein, X represents a linear or branched lower alkylene chain, and p represents 1 or 0. At least one of Y and Y' is the general formula () and the other is an amino lower alkyl group or hydrogen. {However, R ₁ and R ₂ are hydrogen, lower alkoxy group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group,
Lower or higher alkyl group, lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamino lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group or halogen atom-substituted phenyl group, or benzyl group or nitro group-substituted benzyl group). R ₃ and R ₄ are hydrogen, hydroxyl group, lower alkyl group, phenyl group or halogen atom-substituted phenyl group, -OM group (M is a metal atom),
Including cases where -COOM group or any of them is bonded to A. A is hydrogen, hydroxyl group, -COOR ₆ group,
or -OM group, including the case where it is bonded to either _R3 or _R4 . l, m and n represent 0 or 1. However, if n is 0,

The group represented by [Formula] is one hydrogen. R and R' are a cyano group and a _-COR5 group ( _R5 represents an amino group or a lower alkylamino group, including the case where R and R' are combined via -NH- or -NHNH-). or -COOR ₆ group. }] is provided. The method for producing the dithiocarbamate of the present invention will be described below. The dithiocarbamate of the present invention is produced by reacting the raw material N-substituted polyamine with carbon disulfide in water or an organic solvent such as alcohol, dimethylformamide (DMF), or dimethyl sulfoxide (DMSO). It is produced by neutralizing with water or the like to produce a soluble salt of dithiocarbamic acid, which is then metathesized with a soluble salt consisting of a divalent or higher metal. This is illustrated using a simple reaction example as follows. This reaction can be carried out either by dropping carbon disulfide into a mixed solution of substituted polyamines and a neutralizing agent or by dropping substituted polyamine into a mixed solution of carbon disulfide and a neutralizing agent. Can be done. The reaction temperature is preferably in the range of 0 to 70°C, but in this case heat is generated, so it is necessary to control this by adjusting the dropping rate or by external cooling. Although there are various methods for producing the N-substituted polyamine, which is a raw material compound, the following method is usually used. For example, there is a method in which a polyamine is subjected to an addition reaction with a monoethylenically unsaturated compound or an epoxy compound, or a method in which a halogenated compound is subjected to a substitution reaction in a polyamine. These reactions may be carried out without a solvent or with water or an organic solvent such as alcohols, acetone, ethers, dimethylformamide, dimethyl sulfoxide, hexamethylene phosphoramide, or the like. These reactions are briefly shown below. or In the case of a substitution reaction, the reaction is as follows. The polyamines used in the present invention include alkylene diamines, polyalkylene polyamines, hydrazine, etc. Specific examples include ethylene diamine, 1,2-propylene diamine,
1,3-propylene diamine, 1,2-diaminobutane, 2,3-diaminobutane, 1,2-diamino-2-methylpropane, 1,3-diamino-
2-methylpropane, 1,2-diamino-2,2
-dimethylethane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,12-diaminododecane,
1,2-diamino-2-methylbutane, 1,2-
Diaminopentane, 1,2-diaminohexane,
1,2-diaminoheptane, 1,2-diaminooctane, 2,3-diaminopentane, 2,3-diaminohexane, 2,3-diaminoheptane,
2,3-diaminooctane, 1,2-diamino-
2-methylpentane, 2,3-diamino-3-methylpentane, 1,2-diamino-2-ethylbutane, 1,2-diamino-2-methylhexane,
1,2-diamino-2-ethylpentane, 3,4
-diaminohexane, 1,2-diamino-3-methylbutane, hydrazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2,5-diamino-2,5-dimethylhexane, bisaminoethylpropylenediamine, methylenediamine, etc. can be mentioned. To prepare N-substituted polyamines from the above polyamines, itaconic acid and its functional derivatives, maleic acid and its functional derivatives, fumaric acid and its functional derivatives, citraconic acid and its functional derivatives, mesaconic acid and Functional derivatives thereof, 1,2-dicarboxyacetylene and functional derivatives thereof, especially monoethylenically unsaturated compounds such as esters, amides, nitrile salts thereof, or epoxy compounds are subjected to an addition reaction. Specific examples of these compounds reacted with the polyamines mentioned above include sodium fumarate, potassium fumarate, ammonium fumarate, lithium fumarate, calcium fumarate, magnesium fumarate, trimethylammonium fumarate, triethylammonium fumarate, fumarate. Triethanolammonium acid, sodium-potassium fumarate, sodium-ammonium fumarate, monosodium fumarate, monopotassium fumarate, monoammonium fumarate, monolithium fumarate, fumaric acid, methyl fumarate, ethyl fumarate, fumaric acid propyl, isopropyl fumarate,
Butyl fumarate, sec-butyl fumarate, tert-butyl fumarate, pentyl fumarate, hexyl fumarate, heptyl fumarate, octyl fumarate, decyl fumarate, dodecyl fumarate, hexadecyl fumarate, octadecyl fumarate, fumaric acid Vinyl, allyl fumarate, butenyl fumarate, hydroxyethyl fumarate, ethoxyethyl fumarate, dimethylaminoethane fumarate, phenyl fumarate, chlorphenyl fumarate, tolyl fumarate, methoxyphenyl fumarate, benzyl fumarate, fumarate Chlorbenzyl acid, sodium maleate, potassium maleate, ammonium maleate, lithium maleate, calcium maleate, magnesium maleate, trimethylammonium maleate, triethanolammonium maleate, tetramethylammonium maleate, sodium-potassium maleate , sodium-ammonium maleate, monosodium maleate, monopotassium maleate, monoammonium maleate, monolium maleate, maleic acid, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, octyl maleate, maleate Octadecyl acid, hydrazide maleate, sodium itaconate,
Potassium itaconate, ammonium itaconate,
Lithium itaconate, calcium itaconate,
Magnesium itaconate, trimethylammonium itaconate, sodium-potassium itaconate, sodium-ammonium itaconate, potassium-ammonium itaconate, monopotassium itaconate, monosodium itaconate, monoammonium itaconate, itaconic acid, methyl itaconate, itacon Ethyl acid, propyl itaconate,
Isopropyl itaconate, butyl itaconate, sec-butyl itaconate, tertiary-butyl itaconate, pentyl itaconate, (1-methyl)butyl itaconate, (1-ethyl)propyl itaconate, hexyl itaconate, heptyl itaconate, Octyl itaconate, nonyl itaconate, decyl itaconate, undecyl itaconate, dodecyl itaconate, tridecyl itaconate, tetradecyl itaconate, pentadecyl itaconate, hexadecyl itaconate, octadecyl itaconate, vinyl itaconate, allyl itaconate, itaconate Butenyl, hydroxyethyl itaconate, methoxyethyl itaconate, ethoxyethyl itaconate, dibutylaminoethyl itaconate, phenyl itaconate, tolyl itaconate, methoxyphenyl itaconate, benzyl itaconate, chlorbenzyl itaconate, sodium citraconate , Potassium Citraconate, Ammonium Citraconate, Trimethylammonium Citraconate, Triethanolammonium Citraconate, Tetramethylammonium Citraconate, Lithium Citraconate, Calcium Citraconate, Magnesium Citraconate, Sodium-Potassium Citraconate, Sodium Ammonium Citraconate, Citraconate Acid monosodium, monopotassium citraconate, monoammonium citraconate, monolithium citraconate, citraconic acid, methyl citraconate, ethyl citraconate, propyl citraconate, butyl citraconate, octyl citraconate, dodecyl citraconate, hydroxyethyl citraconate , allyl citraconate, dibutylaminoethyl citraconate, phenyl citraconate, benzyl citraconate, p-methylbenzyl citraconate, chlorbenzyl citraconate, ethoxyethyl citraconate, methoxypropyl citraconate, sodium mesaconate, potassium mesaconate, Ammonium mesaconate, lithium mesaconate, trimethylammonium mesaconate, sodium-potassium mesaconate, potassium-ammonium mesaconate, monosodium mesaconate, monopotassium mesaconate, monoammonium mesaconate, mesaconate, methyl mesaconate, ethyl mesaconate , propyl mesaconate, butyl mesaconate, octyl mesaconate, sodium 3-sodiumoxycarbonyl-2,3-epoxypropionate, methyl 3-methoxycarbonyl-2,3-epoxypropionate, 3-ethoxy-2,3
-Ethyl epoxypropionate, propyl 3-propoxycarbonyl-2,3-epoxypropionate, butyl 3-butoxycarbonyl-2,3-epoxypropionate, octyl 3-octyloxycarbonyl-2,3-epoxypropionate, 3 -carboxy-2,3-epoxypropionic acid, 3-potassiumoxycarbonyl-2,3-
Potassium epoxypropionate, sodium 3-sodiumoxycarbonyl-3,4-epoxylactate, 3-carboxy-3,4-epoxylacic acid, methyl 3-methoxycarbonyl-3,4-epoxylactate, 3-ethoxycarbonyl -3,4
-Ethyl epoxy lactate, propyl 3-propoxycarbonyl-3,4-epoxy lactate, butyl 3-butoxycarbonyl-3,4-epoxy lactate, sodium phenyl maleate, potassium phenyl maleate, phenyl maleic acid Ammonium, lithium phenylmaleate, trimethylammonium phenylmaleate, sodium-potassium phenylmaleate, phenylmaleic acid, p-chlorophenylmaleic acid, m-chlorophenylmaleic acid, o-chlorophenylmaleic acid acid, sodium p-chlorophenyl maleate, sodium m-chlorophenyl maleate,
Sodium o-chlorophenyl maleate, p-
Sodium bromphenyl maleate, sodium p-iodophenyl maleate, sodium 2,4-dichlorophenyl maleate, sodium 2,5-dichlorophenyl maleate, 2,6-
Sodium dichlorophenyl maleate, 3,5
- Sodium dichlorophenyl maleate, 3,
Sodium 4-dichlorophenylmaleate,
Sodium 2,3-dichlorophenyl maleate, sodium trichlorophenyl maleate,
Sodium tetrachlorphenyl maleate, p
-Sodium chlorofumarate, sodium p-tolyl fumarate, methyl p-chlorofumarate, p-
Ethyl chlorofumarate, sodium acetylene dicarboxylate, potassium acetylene dicarboxylate,
Ammonium acetylene dicarboxylate, sodium-potassium acetylene dicarboxylate, acetylene dicarboxylic acid, methyl acetylene dicarboxylate, ethyl acetylene dicarboxylate, propyl acetylene dicarboxylate, butyl acetylene dicarboxylate, octyl acetylene dicarboxylate, dodecyl acetylene dicarboxylate, 1,1- Dicarboxyethylene, 1,1-disodiumoxycarbonylethylene, 1,1-dipotassiumoxycarbonylethylene, 1,1-diammoniumoxycarbonylethylene, 1,1-ditrimethylammoniumoxycarbonylethylene, 1,1-dimethoxycarbonylethylene Ethylene, 1,1-diethoxycarbonylethylene, 1,1-dipropoxycarbonylethylene, 1,1-diisopropoxycarbonylethylene, 1,1-dibutoxycarbonylethylene, 1,1-dioctyloxycarbonylethylene, benzalmalonic acid , methyl benzalmalonate, ethyl benzalmalonate, isopropyl benzalmalonate, butyl benzalmalonate,
Hexyl benzalmalonate, octyl benzalmalonate, dodecyl benzalmalonate, sodium benzalmalonate, potassium benzalmalonate,
Ammonium benzalmalonate, lithium benzalmalonate, sodium-potassium benzalmalonate, p-chlorobenzalmalonic acid, sodium p-chlorobenzalmalonate, potassium p-chlorobenzalmalonate, ammonium p-chlorobenzalmalonate, p-chlorobenzalmalonate - lithium chlorbenzalmalonate, sodium dichlorobenzalmalonate,
Sodium trichlorobenzalmalonate, sodium brombenzalmalonate, sodium p-tolylbenzalmalonate, sodium p-methoxybenzalmalonate, sodium p-nitrobenzalmalonate, oxalacetic acid, sodium oxalacetate, oxalacetic acid Potassium, ammonium oxalacetate, lithium oxalacetate, dimethyloxalacetate, sodium diethyloxalacetate, sodium disodium oxalacetate, sodium dipropyloxalacetate, sodium diisopropyloxalacetate, sodium dibutyloxalacetate, dioctyloxal Sodium acetate, sodium didodecyloxalacetate, sodium diallyloxalacetate, di(2-hydroxyethyl)
Sodium oxalacetate, disodium methoxymethylenemalonate, disodium ethoxymethylenemalonate, disodium isopropoxymethylenemalonate, disodium propoxymethylenemalonate, disodium butoxymethylenemalonate, disodium octyloxymalonate, methoxymethylenemalonate dimethyl acid, diethyl ethoxymethylenemalonate, diisopropyl isopropoxymethylenemalonate, dipropyl propoxymethylenemalonate, dibutyl butoxymethylenemalonate, dioctyloxymethylenemalonate, didodecyl didodecyloxymethylenemalonate, diallyloxymethylenemalonate, 3-anilinomalonic acid; sodium 3-anilinomalonate, potassium 3-anilinomalonate,
Ammonium 3-anilinomalonate, lithium 3-anilinomalonate, tetramethylammonium 3-anilinomalonate, methyl 3-anilinomalonate, ethyl 3-anilinomalonate, aconitic acid, trisodium aconitate, tripotassium aconitate, triammonium aconitate,
Trilithium aconitate, trimethylammonium aconitate, tetramethylammonium aconitate, trimethyl aconitate, triethyl aconitate, triisopropyl aconitate, tripropyl aconitate, tributyl aconitate, trioctyl aconitate, tridecyl aconitate, triallyl aconitate, 3-
p-Chloranilinomalonic acid, sodium 3-p-chloroanilinomalonate, disodium transglutaconate, dipotassium trans-glutaconate, diammonium trans-glutaconate,
Trans-dilithium glutaconate, trans-
ditetramethylammonium glutaconate, dimethyl trans-glutaconate, diethyl trans-glutaconate, dipropyl trans-glutaconate, diisopropyl trans-glutaconate,
Dibutyl trans-glutaconate, dioctyl trans-glutaconate, didodecyl trans-glutaconate, cis-glutaconic acid, disodium cis-glutaconate, dipotassium cis-glutaconate, diammonium cis-glutaconate, dilithium cis-glutaconate, cis -Ditrimethylammonium glutaconate, methyl cis-glutaconate, ethyl cis-glutaconate, propyl cis-glutaconate, isopropyl cis-glutaconate, butyl cis-glutaconate, octyl cis-glutaconate, octadecyl cis-glutaconate, α -dihydromuconic acid, sodium α-dihydromuconate, potassium α-dihydromuconate,
α-Ammonium dihydromuconic acid, α-dihydromuconic acid tetramethylammonium, α-dihydromuconic acid sodium-potassium, α-methyl dihydromuconate, α-ethyl dihydromuconate, α-dihydromuconic propyl, α-dihydromuconic acid isopropyl, α-dihydromuconic acid Butyl, octyl α-dihydromuconic acid, dodecyl α-dihydromuconic acid, β-dihydromuconic acid, sodium β-dihydromuconic acid, potassium β-dihydromuconic acid, ammonium β-dihydromuconic acid, lithium β-dihydromuconic acid, trans-transmuconate, trans - Sodium trans-muconate, Potassium trans-trans muconate, Ammonium trans-trans muconate, Methyl trans-trans- muconate, Ethyl trans-trans- muconate, Propyl trans-trans- muconate, Trans-
Trans-butyl muconate, cis-cis-muconic acid, sodium cis-cis-muconic acid, potassium cis-cis-muconate, ammonium cis-cis-muconic acid, methyl cis-cis-muconic acid, cis-cis-muconic acid Ethyl, cis-trans-muconic acid, sodium cis-trans-muconic acid, methyl cis-trans-muconic acid, 1,1,2-tricarboxyethylene, 1,1,2-trisodiumoxycarbonylethylene, 1,1 , 2-trimethoxycarbonylethylene, 1,1,3-tricarboxypropene-1, 1,1,3-trisodiumoxycarbonylpropene-1,1,
1,3-trimethoxycarbonylpropene-1,
1,1,3-triethoxycarbonylpropene-
1,1,1,3-triisopropoxypropene-
1,1,1,3-tributoxycarbonylpropene-1,1,5-dicarboxypentene-1,
1,5-disodiumoxycarbonylpentene-1, 1,5-dipotassiumoxycarbonylpentene-1, 1,5-dimethoxycarbonylpentene-1, 1,5-diethoxycarbonylpentene-1,1,5-diiso Propoxycarbonylpentene-1, 1,5-dibutoxycarbonylpentene-1, 1,3-dicarboxy-2-methylpropene-1, 1,3-disodiumoxycarbonyl-2-methylpropene-1,1,3 -dimethoxycarbonyl-2-methylpropene-1,1,3
-diethoxycarbonyl-2-methylpropene-
1,1,3-dipropoxycarbonyl-2-methylpropene-1, 1,3-dibutoxycarbonyl-2-methylpropene-1, 1,3-dioctyloxycarbonyl-2-methylpropene-1,
1,3-dicarboxy-1-methylpropene-
1,1,3-disodiumoxycarbonyl-1
-Methylpropene-1,1,3-dimethyloxycarbonyl-1-methylpropene-1, hydroxymaleic acid, sodium hydroxymaleate, potassium hydroxymaleate, ammonium hydroxymaleate, lithium hydroxymaleate, trimethylammonium hydroxymaleate , sodium-potassium hydroxymaleate, potassium-ammonium hydroxymaleate, methyl hydroxymaleate, ethyl hydroxymaleate, propyl hydroxymaleate, butyl hydroxymaleate, hexyl hydroxymaleate, octyl hydroxymaleate, dodecyl hydroxymaleate, Octadecyl hydroxymaleate, hydroxymafumaric acid, sodium hydroxyfumarate, potassium hydroxyfumarate, ammonium hydroxyfumarate, lithium hydroxyfumarate, trimethylammonium hydroxyfumarate, tetramethylammonium hydroxyfumarate, methyl hydroxyfumarate, hydroxyfumarate Ethyl acid, propyl hydroxy fumarate, butyl hydroxy fumarate, octyl hydroxy fumarate, dodecyl hydroxy fumarate, octadecyl hydroxy fumarate, allyl hydroxy fumarate, dihydroxy maleic acid, sodium dihydroxy maleate, potassium dihydroxy maleate, dihydroxy maleic acid Ammonium, methyl dihydroxy maleate, ethyl dihydroxy maleate dihydroxy fumarate, sodium dihydroxy fumarate, potassium dihydroxy fumarate, ammonium dihydroxy fumarate, potassium dihydroxy fumarate, ammonium dihydroxy fumarate, lithium dihydroxy fumarate, methyl dihydroxy fumarate, Ethyl dihydroxy fumarate, propyl dihydroxy fumarate, butyl dihydroxy fumarate, dodecyl dihydroxy fumarate, fumaric acid amide, maleic acid amide, itaconic acid amide, citraconic acid amide, mesaconic acid amide, fumaric acid N-methyl amide, maleic acid N
-methylamide, itaconic acid N-methylamide,
Citraconic acid N-methylamide, Mesaconic acid N-
Methylamide, fumaric acid N-ethylamide, maleic acid N-ethylamide, itaconic acid N-ethylamide, fumaric acid N-butylamide, fumaric acid N-ethylamide
-benzylamide, maleic acid N-benzylamide, itaconic acid N-benzylamide, mesaconic acid N-benzylamide, citraconic acid N-benzylamide, fumaric acid nitrile, maleic acid nitrile, mesaconic acid nitrile, itaconic acid nitrile,
citraconic acid nitrile, maleimide, fumarimide, itaconimide, mesaconimide, citraconimide, benzylidene malonic acid amide, p
- Chlorbenzylidenemalonamide, benzylidenemalononitrile, p-chlorobenzylidenemalononitrile, aconitic acid triamide, aconitic acid trinitrile, trans-glutaconic acid amide, trans-glutaconic acid nitrile, cis-
Glutaconamide, cis-glutaconic acid nitrile, α-dihydromuconic acid amide, α-dihydromuconic acid nitrile, trans-trans-muconic acid amide, trans-trans-muconic acid nitrile, 1,1,3-triaminocarbonylpropene-1 , 1,1,3-trinitrilepropene-1,
1,3-diaminocarbonyl-2-methylpropene-1, 1,3-dicyano-2-methylpropene-1, hydroxymaleic acid amide, hydroxymaleic acid nitrile, dihydroxymaleic acid amide, dihydroxyfumaric acid amide, dihydroxymaleic acid Examples include nitrile, dihydroxyfumaric acid nitrile, maleic acid monoamide, fumaric acid monoamide, itaconic acid monoamide, citraconic acid monoamide, mesaconic acid monoamide, and the like. The above addition reaction is carried out at 0-150°C, preferably at 30°C.
This can be easily carried out by dropping the monoethylenically unsaturated compound or epoxy compound into an excess polyamine or a solution thereof in water or an inert solvent at a temperature in the range of -80°C. The reaction temperature, which normally occurs during this reaction, can be controlled by adjusting the dropwise addition rate of the above-mentioned compound; however, if the heat generation is severe, the temperature can be controlled by cooling the reaction vessel. After the addition reaction is completed in this way, the excess polyamine is recovered under reduced pressure to quantitatively obtain the N-substituted polyamine. On the other hand, reducing the excess amount of polyamine,
It is also possible to obtain an addition reaction product containing N,N'-disubstituted polyamine as a main component by increasing the dropping rate of the ethylenically unsaturated compound or epoxy. At this time, if one or more N-substituted polyamines are produced, they can be separated and purified into N-mono-substituted polyamines, N,N'-disubstituted polyamines, etc. by distillation or the like. These N-monosubstituted polyamines and N,N'-disubstituted polyamines are used as starting materials for the present invention, but without separating and purifying both of them and the addition reaction product,
It is also possible to use the N-substituted polyamine as a raw material as it is, and this can be said to be a preferable method. Furthermore, N-monodithiocarbamoylamine, which is obtained by introducing a dithiocarbamoyl group into the above-mentioned amine, can also be used in these addition reactions. The method for producing these N-monodithiocarbamoylamines is to produce inner salts according to the method of org.synth.col.vol. () p. 394, and then treat them with an equivalent amount of alkali to produce these water-soluble salts. is obtained and can be used as a raw material amine in the present invention. This is briefly illustrated by a reaction example as follows. N-monodithicarbamoyl polyamines can be obtained from all of the polyamines mentioned above, but specific examples are as follows. 2-Aminoethyldithiocarbamic acid, 2-aminopropyldithiocarbamic acid, 3-aminopropyldithiocarbamic acid, 2-aminobutyldithiocarbamic acid, 2-amino-1-methyldithiocarbamic acid, 3- Amino-2-methyldithiocarbamic acid, 2-amino-2,2-dimethyldithiocarbamic acid, 4-aminobutyldithiocarbamic acid, 6-aminohexyldithiocarbamic acid, N-dithiocarbamoyldiethylenetriamine, N- Examples include dithiocarbamoyltriethylenetetramine, N-dithiocarbamoylpolyethyleneimine, and N-aminodithiocarbamic acid. These N-monodithiocarbamoyl polyamines can be used as free acids, soluble salts, ammonium salts, esters, etc. The addition reaction between N-monodithiocarbamoylpolyamine and an ethylenically unsaturated compound or epoxy compound can be carried out using equivalent amounts of both, so there is no need to use an excess of N-monodithiocarbamoylpolyamine like the polyamine mentioned above. do not have. Therefore, a collection process is not necessary. When the functional derivative is an ester, in the former method using an excess of polyamine, generally N
-The reaction may not be completed with substituted polyamines, and further cyclization or substitution reactions may occur, so piperazine-
2-one derivatives, polymers, etc. are often produced. Therefore, when the functional derivative is an ester, N-substituted polyamines can be obtained by using N-monodithiocarbamoyl polyamines instead of polyamines, which is a desirable method. On the other hand, the N-substituted polyamine of the present invention can also be produced by subjecting the polyamine to a substitution reaction with a halogenated compound, neutralizing the hydrogen halide produced as a by-product with an alkali, and then performing a purification treatment as necessary. It is possible. The halides used in this reaction also include compounds obtained by adding hydrogen halide to the compounds specifically exemplified as the ethylenically unsaturated compounds or epoxy compounds. Typical specific examples include the following. Sodium chlorosuccinate, potassium chlorosuccinate, ammonium chlorosuccinate, lithium chlorosuccinate, chlorsucciamide, chlorosuccinimide, chlorsuccinic hydrazide,
Nitrile chlorosuccinate, methyl chlorosuccinate, ethyl chlorosuccinate, allyl chlorosuccinate, 1,2-(disodiumoxycarbonyl)-
3-chloropropane, 1,2-(dipotassiumoxycarbonyl)-3-chloropropane, 1,2-
(diammoniumoxycarbonyl)-3-chloropropane, 1,2-(diaminocarbonyl)-3-
Chlorpropane, 1,2-dicyano-3-chloropropane, 1,2-(dimethoxycarbonyl)-3
-Chlorpropane, 1,2-(disodiumoxy)-2-chloropropane, 1,2-(dipotassiumoxycarbonyl)-2-chloropropane, 1,
2-(diaminocarbonyl)-2-chloropropane, 1,2-dicyano-2-chloropropane,
1,2-(dimethoxycarbonyl)-2-chloropropane, 2-chloromethylmalonic acid, sodium 2-chloromethylmalonate, potassium 2-chloromethylmalonate, ammonium 2-chloromethylmalonate, 2-chloromethylmalonate lithium oxide,
2-chloromethylmalonic acid amide, 2-chloromethylmalononitrile, methyl 2-chloromethylmalonate, 2-chloromethylmalonate ethyl, 2-
Allyl chloromethylmalonate, chlormalonic acid,
Sodium chlormalonate, potassium chlormalonate, ammonium chlormalonate, lithium chlormalonate, chlormalonamide, chlormalonic acid imide, chlormalononitrile, methyl chlormalonate, ethyl chlormalonate, octyl chlormalonate, allyl chlormalonate, 1,3
-dicarboxy-2-chloropropane, 1,3-
disodium oxy-2-chloropropane, 1,
3-dipotassiumoxy-2-chloropropane,
1,3-diaminocarbonyl-2-chloropropane, 1,3-dicyano-2-chloropropane,
1,3-dimethoxycarbonyl-2-chloropropane, 1,3-disodiumoxy-tochlorpropane, 1,3-dipotassiumoxycarbonyl-
1-chloropropane, 1,3-diaminocarbonyl-1-chloropropane, 1,3-dicyano-1
-chloropropane, 1,3-dimethoxycarbonyl-1-chloropropane, 1,3-diethoxycarbonyl-1-chloropropane, and the like. This substitution reaction is also carried out at 0-150°C, preferably at 30-150°C.
This can be carried out by dropping the halogenated alkyl derivative into excess polyamine at a temperature range of 80°C. This reaction is generally accompanied by intense heat generation, but the temperature is controlled by adjusting the dropwise addition rate of the alkyl halide derivative and cooling the reaction vessel. After the dropwise addition of the halogenated alkyl derivative is completed, heating is continued and maintained at a constant temperature to complete the substitution reaction. Neutralization of the by-product hydrohalic acid in the obtained reaction product can be easily carried out with alkali hydroxide, but it is more advantageous to introduce ammonia gas. Next, by recovering excess polyamine from the reaction product under reduced pressure, the target N-monosubstituted polyamine is quantitatively obtained, which is purified by distillation or the like. This reaction is usually carried out using an excess of polyamine, but it is possible to produce an N-disubstituted polyamine in which two identical substituents have been introduced by reducing the amount of polyamine and adjusting the dropping rate and reaction temperature. is also possible, and this is exactly the same as in the case of the addition reaction described above. In the present invention, by using an N-monosubstituted polyamine as a raw material instead of the above-mentioned polyamine raw material, N-,
N'-disubstituted polyamines can also be produced.
Also useful are N-substituted polyamines obtained by reacting polyamines with compounds containing two or more reactive functional groups. Specific examples of the polyfunctional compound include glycidyl itaconate, glycidyl maleate, glycidyl fumarate, glycidyl citraconate, glycidyl mesaconate, and the like. This reaction also contains 0 to 0 in excess polyamine.
This is carried out by dropping the polyfunctional compound at a temperature of 150 DEG C., preferably from 30 DEG to 80 DEG C., and the same number of polyamines as the number of functional groups is introduced into the resulting N-substituted polyamine. The desired N-substituted polyamine is prepared by recovering excess polyamine and neutralizing by-product hydrohalic acid, if present. N-substituted polyamines produced by the various methods described above serve as starting materials for the present invention. Neutralizing agents used in the present invention include, for example, alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, ammonia, aqueous ammonia, and methylamine. ,
Examples include dimethylamine and ethanolamine. Various means are used for producing these dithiocarbamate metal salts. For example, a water-soluble metal salt to be metathesized may be added to a water-soluble salt solution of dithiocarbamic acid represented by the above general formula, or vice versa, to form a precipitate, or both may be added to a reaction tank at the same time. It's okay. Water is usually used as the solvent, but there is no particular limitation as long as it dissolves the solute in this reaction.Specifically, water, pyridine, methanol, ethanol, isopropyl alcohol, N-methyl-2-pyrrolidone, sulfolane, and dimethyl are used. Examples include formamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, dioxane, acetone, and tetrahydrofuran, and a mixed solvent of two or more of these may also be used. Reaction temperature is 0~70℃
The range shall be . The dithiocarbamate metal salts thus produced are generally isolated as solids, even if they contain water of crystallization and/or solvent. The by-produced inorganic salts can be easily removed by washing with water after removing the reaction solvent, but this step may be omitted if the inorganic salts are practically harmless. The dithiocarbamate metal salt obtained by this reaction may be a salt in which other types of metals are complexed; for example, a dithiocarbamate metal salt in which a manganese salt is complexed with zinc or the like is also included in the present invention. Next, the soluble metal salts used in metathesis are zinc, manganese, iron, nickel, tin, cobalt,
It is made of a metal having a valence of two or more, such as calcium, magnesium, or copper, and is sometimes used as a mixed solution of two or more of these. Specifically, soluble metal salts include zinc chloride, zinc sulfate,
Zinc nitrate, zinc acetate, manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, copper chloride, copper sulfate, copper nitrate, copper acetate, iron chloride, iron sulfate, iron nitrate,
Iron acetate, nickel chloride, nickel sulfate, tin chloride, tin sulfate, tin nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, calcium chloride, calcium oxide, calcium nitrate, magnesium chloride,
Examples include magnesium nitrate. The specific examples used in the above description of the N-substituted polyamine and water-soluble metal salt are merely used to explain the present invention, and the present invention is not limited to these. Although the metal salts obtained by these metathesis are described above in the form of a single compound, they can also be expressed in the form of a metal-mediated polymer. Generally, it cannot be defined for this type of compound. The dithiocarbamate metal salt of the present invention is generally stable at room temperature. However, it tends to gradually decompose at high temperatures or during long-term storage, but by adding stabilizers it is possible to obtain a product with further improved stability. Stabilizers may be added during production or during formulation. Stabilizers include urea, paraformaltehyde, hexamethylenetetramine, O-tolyl biguanide, diphenylguanidine, diaminotoluene, 1,8-3,6-diedomethylene-1,
3,6,8-tetraazacyclodecane, N,
N'-dimethylol urea, 1,3,5-tris(cyanomethyl)hexahydrotriazine, N-
Examples include methylurea and N,N'-dimethylurea. The dithiocarbamate of the present invention has low toxicity to the human body and useful plants, does not leave behind substances that have harmful effects on the human body and useful plants after use, and is generally free from phytotoxicity when used for agricultural and horticultural purposes. , and has a high pest control effect. In addition, in the case of soluble salts, they have an immediate effect but have the disadvantage of lacking in residual effect.
Cases of drug damage often occur. In use, the agent of the present invention can be applied directly as it is, but it can be prepared as an aqueous solution by using an appropriate liquid carrier, solid carrier, emulsifying dispersant, etc. according to the agricultural chemical formulation method known in the art. It can be applied in any form such as a powder, a wettable powder, a granule, an emulsifier, a flowable agent, a flow dust agent, a tablet, an oil solution, a suspension, a foaming agent, and a spray. These carriers include water, alcohol, benzene, xylene, toluene, alkylnaphthalene, cyclohexane, paraffin, ether, ester, acetone, methyl ethyl ketone, methyl isobutyl ketone, kerosene, freon, clay, talc, kaolin, bentonite, acid clay, and silica. soil, calcium carbonate, white carbon, quartz alumina,
Examples include methylcellulose, starch, gum arabic, polyvinyl alcohol, polyvinyl acetate, and the like. In addition, auxiliary agents commonly used in formulations, such as surfactants such as spreading agents, emulsifiers, and dispersants, include soaps, higher alcohol sulfates, alkyl sulfonates, alkylaryl sulfonates, and surfactants. Quaternary ammonium salts, polyalkylene oxides, lignin sulfonates, and the like can be appropriately blended. The compounds of the present invention are bactericidal, bactericidal, insecticidal, acaricidal,
It can also be used as a weed killer, plant growth regulator, etc. Furthermore, when used for industrial purposes, it is possible to prevent contamination and damage caused by mold and other microorganisms that occur in the paint film, and also to prevent contamination by slime, algae, etc. that occur in cooling water, etc. The present invention will be explained in more detail using specific examples, but the present invention is not limited to these specific examples. Examples of producing the dithiocarbamate of the present invention will be described below. Production Examples 1 to 21 N-[1,2-
Add 38.5 g (0.15 mol) of di(sodiumoxycarbonyl)ethyl]ethylenediamine. Add 50ml of water to this and continue stirring at room temperature.
22.8 g (0.30 mol) of carbon disulfide was gradually added dropwise. As the temperature of the reaction solution rose with the dropwise addition, the temperature was maintained below 38°C in a water bath, and after the completion of the dropwise addition, stirring was continued while maintaining the temperature at 35-38°C for an additional 2 hours. Next, 25 g (0.30 mol) of a 48% caustic soda aqueous solution was gradually added dropwise to this reaction solution while keeping the temperature below 42°C in a water bath, and after the dropwise addition was completed, stirring was continued for 2 hours at a temperature of 38 to 42°C. Subsequently, a clear yellow concentrated aqueous solution of sodium N-[1,2-di(sodiumoxycarbonyl)ethyl]ethylenebisdithiocarbamate was obtained. Yield: 137g
The active ingredient content was 45.6%. and c/3
-The structure was confirmed by NMR. In addition, the compounds of Production Examples 2 to 21 were obtained in the same manner as above, except that the N-substituted polyamine was changed, and in the presence of an alkali or ammonia.

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S

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solid

(−NCSS−)

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solid

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solid state




Production example 22-35 Attached stirrer, thermometer and dropping funnel
In a 500 ml three-necked flask, add 79 g (0.25 g) of a 50% aqueous solution of sodium 2-aminoethyldithiocarbamate.
mol) and stir at room temperature. A mixed solution of 36 g (0.25 mol) of maleic acid dimethyl ester and 40 ml of methanol was gradually added dropwise to the mixture while stirring at room temperature. After the dropwise addition, stirring is continued for 2 hours at 30-35°C, resulting in a thick orange transparent solution. 19 g (0.25 mol) of carbon disulfide was added dropwise to this solution while keeping it at 35°C, followed by 20.7 g of a 48% caustic soda aqueous solution.
(0.25 mol) dropwise. 1 at 35℃ after dropping
After stirring for an hour, 191 g of a yellow-orange transparent sodium N-[1,2-di(methoxycarbonyl)ethyl]ethylenebisdithiocarbamate aqueous solution was obtained.
Its active ingredient was 50.3%. and C/3-
Its structure was confirmed by NMR. In addition, by the same treatment method as above, the compounds of Production Examples 23 to 35 were obtained by changing the N-substituted polyamine and in the presence of an alkali or ammonia.

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[Table] Production examples 36 to 96 with stirrer, thermometer and dropping funnel installed
29 g (0.03 mol) of a 50% aqueous solution of sodium N-[1,2-di(n-butoxycarbonyl)ethyl]ethylenebisdithiocarbamate and 200 ml of water were added to a 500 ml four-necked flask, and stirred at room temperature until uniform. It was made into an aqueous solution. Next, add 8.6 g (0.03 mol) of a 47% zinc chloride aqueous solution to this solution while stirring at room temperature.
The mixture was gradually added dropwise over 30 minutes, and stirring was continued for an additional 3 hours at room temperature. The slurry obtained by this metathesis reaction was filtered under reduced pressure by suction, and then washed three times with 200 ml of water to obtain a pale yellow filter cake. This cake was dried at 40-50°C under reduced pressure of 2-10 mmHg to obtain 17 g of zinc N-[1,2-di(n-butoxycarbonyl)ethyl]ethylenebisdithiocarbamate. The structure was also confirmed by C/3-NMR. Moreover, by the same treatment method as above, by changing the N-substituted polyamine and the water-soluble metal salt, compounds of Production Examples 37 to 96 were obtained by metathesis reaction.

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body ｜

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｜

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body ｜

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｜

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body ｜

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｜

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｜




Production Example 97 27.2 g (0.1 mol) of a 50% aqueous zinc chloride solution and ethanol were mixed and stirred to form a homogeneous solution, and N-{1,2-
After dropping 33.8 g (0.05 mol) of a 50% aqueous solution of sodium di(sodiumoxycarbonyl)ethylhydrazinebisdithiocarbamate, stirring was continued for an additional 2 hours at room temperature. The generated slurry was filtered under reduced pressure, washed with ethanol, and heated to a temperature of 40°C.
Dry under ~50℃ and 10mmHg vacuum to obtain white N-
{1,2-di(zincoxycarbonyl)ethyl}
24 g of zinc hydrazine bisdithiocarbamate was obtained. The following structure was confirmed by C/3-NMR.

[Table] Production examples 98-102 N-{1,2- in a 500 ml beaker in a nitrogen stream
11 g of 20% slurry of manganese di(ethoxycarbonyl)ethyl}ethylenebisdithiocarbamate
(0.005 mol) and stirred at room temperature.
1.6 g (0.002 mol) of a 20% aqueous zinc sulfate solution was added dropwise. Next, the cake was stirred at room temperature for 2 hours and then filtered, and the cake was dried under reduced pressure to form a pale yellow powder of zinc composite N-{1,
2.3 g of manganese 2-di(ethoxycarbonyl)ethyl}ethylenebisdithiocarbamate was obtained.
As a result of thorough washing with water and analysis, the contents of zinc and manganese were 1.2% and 12.4%, respectively. Infrared absorption spectrum (IR-spectrum)
showed that this substance is a mixture of manganese and zinc salts of dithiocarbamic acid, and not a single zinc salt. In addition, by the same treatment method as above, by replacing the N-substituted ethylene bisdithiocarbamate manganese salt and adding a water-soluble zinc salt, Production Examples 99 to
102 compounds were obtained.

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[Table] Next, examples of formulations of the pesticidal agent of the present invention are listed, but the types of additives and mixing ratios are not intended to limit the present invention, and can be applied in a wider range. be. Formulation Example 1 75 parts of the dithiocarbamic acid heavy metal salt of the present invention, 10 parts of a surfactant, a fixing agent and a dispersing agent, and 15 parts of clay are uniformly mixed and pulverized to 1 to 3 microns to obtain a wettable powder. When using, dilute with water etc. Formulation Example 2 5 parts of the dithiocarbamic acid heavy metal salt of the present invention and 95 parts of clay are uniformly mixed and pulverized to form a powder. When used, it can be applied as is. Formulation Example 3 20 parts of the dithiocarbamate compound of the present invention are mixed with 30 parts of bentonite, 1 part of calcium lignosulfonate, 0.5 parts of sodium laurate, and 48.5 parts of clay, and after adding water and kneading, extrusion is carried out using a screw. Granules, dried to form granules. Formulation Example 4 The aqueous solution of the dithiocarbamate of the present invention in Production Example 1 can be used as an aqueous solvent, and can be used after being diluted with water. Formulation Example 5 40 parts of the dithiocarbamic acid heavy metal salt of the present invention, 50 parts of white carbon, and 10 parts of clay are ground with a dietomizer to prepare a flow dust agent. Formulation Example 6 30 parts of the dithiocarbamate heavy metal salt of the present invention, water
A slurry consisting of 50 parts of surfactant, fixing agent, and 20 parts of dispersing agent is passed through a sand mill to form a flowable agent. Test Example 1 Alternaria cultured on PDA (Peptone Dextrose Agar Plane) medium in advance. Add 0.1 ml of Altarnaria amli spore suspension to 1 ml of the drug solution diluted to the specified concentration, and from this 0.01
Take ml and drop it onto a glass slide. This slide glass was stored in a tray lined with paper containing moisture, and this was placed in a thermostat adjusted to 28℃.
After standing still for 24 hours, it was examined under a microscope and the spore germination rate was calculated. The results are shown in the table below.

[Table] Daisen Z-78 indicates zinc ethylenebisdithiocarbamate. Test Example 2 Each drug was added to a PDA medium at a predetermined concentration to form a flat active plate, and a PDA medium was used as a flat active plate. Pseudomonas Lach-rymans (A), Pseudomonas. Pseudomonas theal (B) and Erwinia. Aloide (Eruwinia)
aroidae:C) was inoculated. After culturing at 25°C for 43 hours,
I conducted an investigation. Those that grew were designated as (+), those that slightly grew (±), and those that did not grow at all (-). The results are shown in the table below.

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[Table] Test example 3 Kiyu cucumbers grown in the iron house (variety:
A diluted solution of the test chemical at a predetermined concentration was sprayed using a small glass sprayer at the time of 1.5 to 2.5 true leaves of Tokiwa Jizo (No. 3, 1 section, 4 series). On the first day after spraying, the plants were inoculated by spraying with a spore suspension of the fungus Sclerosis fungus and placed in a greenhouse (18°C to 25°C) with a humidity of 90% or higher to encourage infection. The investigation was conducted 5 to 7 days after spraying, and the top two leaves developed at the time of spraying were examined for the degree of disease onset (graded from 0 to 4), and the control value was calculated. The results are shown in the table below.

【table】

【table】

[Table] Test example 4 Tomatoes being cultivated in the Firelon house (variety:
A diluted solution of the test chemical at a predetermined concentration was sprayed using a glass sprayer at the time of the 5th true leaf of the 1-section 4-row plant. One day after spraying, a tomato late blight spore suspension was uniformly sprayed for inoculation. It was kept at a high humidity of 90% or more and a temperature of 18 to 25 degrees Celsius. The investigation was conducted on 4 leaves per plant on the 8th day after inoculation. The degree of disease onset was evaluated on a scale of 0 to 4, and the control value was calculated. The results are shown in the table below.

【table】

【table】

[Table] Disease incidence index in untreated area
(4) Drug damage; same as above test example

Claims (1)

[Claims] 1 General formula () () [Wherein, X represents a linear or branched lower alkylene chain, and p represents 1 or 0. At least one of Y and Y' is the general formula () and the other is an amino lower alkyl group or hydrogen. {However, R ₁ and R ₂ are hydrogen, lower alkoxy group, phenyl group,
or -COOR ₆ groups (R ₆ is a metal atom, ammonium group, lower or higher alkyl group, lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamino lower alkyl group, mono or poly hydroxy lower alkyl group, phenyl group, halogen atom-substituted phenyl group, benzyl group, or nitro group-substituted benzyl group). R ₃ and R ₄ are each hydrogen, hydroxyl group, lower alkyl group, phenyl group, halogen atom-substituted phenyl group, -OM group (M is a metal atom), -COOM group, or when any of them is bonded to A. include. A is hydrogen, hydroxyl group, _-COOR6 group or -OM group, _R3 or
Including cases where it is combined with any of R ₄ . l, m,
and n indicates 0 or 1. However, when n is 0, the group represented by the formula is one hydrogen. R and R' are respectively a cyano group and a _-COR5 group ( _R5 represents an amino group or a lower alkylamino group, and R and
This includes the case where R' is combined via -NH- or -NHNH-. ) or -COOR ₆ groups. }]
A salt of dithiocarbamic acid represented by: 2. The salt of dithiocarbamic acid according to claim 1, which is an alkali metal salt or an alkaline earth metal salt. 3. The dithiocarbamic acid salt according to claim 1, which is an ammonium salt or an amine salt. 4 Claim 1 which is a heavy metal salt with a valence of two or more
Salts of dithiocarbamic acids as described. 5 Claim 1 in which a dithiocarbamate, which is a divalent or higher-valent heavy metal salt, is complexed with a different metal.
Salts of dithiocarbamic acids as described. 6 General formula () [Wherein, X is a linear or branched lower alkylene chain, R _q is hydrogen or a dithiocarbonate group, and p is 1 or 0. At least one of Y and Y' is the general formula () and the other is an amino lower alkyl group or hydrogen. {However, R ₁ and R ₂ are each hydrogen, lower alkoxy group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, higher or lower alkyl group, lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamino lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group, halogen atom-substituted phenyl group or benzyl group, or nitro group-substituted benzyl group). R ₃ and R ₄ are
hydrogen, hydroxyl group, lower alkyl group, phenyl group, or halogen atom-substituted phenyl group, respectively;
This includes the case where -OM group (M is a metal atom), -COOM group, or any one of them is bonded to A. A is hydrogen, a hydroxyl group, a _-COOR6 group, or an -OM group, including the case where it is bonded to either _R3 or _R4 . l, m, and n represent 0 or 1. However, when n is 0, the group represented by the formula is one hydrogen. R and R' are a cyano group, _-COR5 group ( _R5 represents an amino group or a lower alkylamino group, and R and R' are -
Including cases of association via NH- or -NHNH-. ) or -COOR ₆ groups. }] and carbon disulfide in the presence of a free base, and if necessary, react with a water-soluble metal salt of divalent or higher valence to cause metathesis () [Wherein, X represents a linear or branched lower alkylene chain, and p represents 1 or 0. At least one of Y and Y' is the general formula () and the other is an amino lower alkyl group or hydrogen. {However, R ₁ and R ₂ are each hydrogen, lower alkoxy group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower or higher alkyl group, lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamine lower alkyl group, mono- or polyhydroxy lower alkyl group, phenyl group or halogen atom-substituted phenyl group, benzyl group or nitro group-substituted benzyl group). R ₃ and R ₄ are
hydrogen, hydroxyl group, lower alkyl group, phenyl group or halogen atom-substituted phenyl group, -
This includes the case where the OM group (M is a metal atom), the -COOM group, or any one of them is bonded to A. A is hydrogen, a hydroxyl group, a _-COOR6 group, or an -OM group, including the case where it is bonded to either _R3 or _R4 . l, m, and n represent 0 or 1. However, when n is 0, the group represented by the formula is one hydrogen. R and R' are cyano group, _-COR5 group ( _R5 is amino group,
It represents a lower alkylamino group, and R and R' are -NH
- or -NHNH-. ) or -COOR ₆ group. }] A method for producing a salt of dithiocarbamic acid. 7 General formula () [Wherein, X represents a linear or branched lower alkylene chain, and p represents 1 or 0. At least one of Y and Y' is the general formula () and the other is an amino lower alkyl group or hydrogen. {However, R ₁ and R ₂ are each hydrogen, lower alkoxy group, phenyl group, or -COOR ₆ group (R ₆ is a metal atom, ammonium group, lower or higher alkyl group, lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, lower alkenyl group, lower alkylamino lower alkyl group, mono- or polyhydroxyalkyl group, phenyl group or halogen atom-substituted phenyl group, benzyl group or nitro group-substituted benzyl group). R ₃ and R ₄ are hydrogen, hydroxyl group, lower alkyl group, phenyl group or halogen atom-substituted phenyl group, -OM
This includes the case where a group (M is a metal atom), a -COOM group, or any of them is bonded to A. A is hydrogen,
Hydroxyl group, -COOR ₆ group, or -OM group, and R ₃
and R ₄ . l, m,
and n indicates 0 or 1. However, when n is 0, the group represented by the formula is one hydrogen. R and R' are cyano group, _-COR5 group ( _R5 is amino group,
It represents a lower alkylamino group, and R and R' are -NH-
or -NHNH-. ) or -COOR ₆ group)}] An agricultural and industrial microbicide characterized by containing as an active ingredient a salt of dithiocarbamic acid. 8. The agricultural and industrial microbicide according to claim 7, which contains an alkali metal salt of dithiocarbamate or an alkaline earth metal salt as an active ingredient. 9. The agricultural and industrial biocide according to claim 7, which contains an ammonium dithiocarbamate salt or an amine salt as an active ingredient. 10. The agricultural and industrial biocide according to claim 7, which contains a divalent or higher valent heavy metal salt of dithiocarbamic acid as an active ingredient. 11. The agricultural and industrial biocidal agent according to claim 7, wherein the active ingredient is a metal salt in which a divalent or higher valent heavy metal salt of dithiocarbamic acid is combined with a different metal.