JPH045282A - New 2-hydrazinobenzothiazole derivative and herbicide comprising the same derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1> is H, 1-6C alkyl or 2-6C alkanoyl; R<2> and R<3> are 1-6C alkyl, 2-4C alkenyl, 3-4C alkynyl, (substituted) aryl or (substituted) pyridinyl; R<4> to R<7> are H, halogen, 1-6C alkyl, 1-6C haloalkyl or 1-6C alkoxy]. EXAMPLE:1-Methyl-1-phenyl-2-(2-benzothiazolyl)hydrazine. USE:A herbicide. PREPARATION:A chlorobenzothiazole shown by formula II is reacted with an acetylhydrazine shown by formula III (Ac is acetyl) optionally in an organic solvent in the presence of a base. (e.g. sodium hydroxide)

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a novel 2-hydrazinobenzothiazole derivative, which has not been described in any literature, and a herbicide containing the same as an active ingredient.

Prior art JP-A-48-72164 discloses synthesis examples of 2-hydrazinobenzothiazole derivatives, but does not describe their herbicidal activity at all.

Structure of the Invention The present inventors have synthesized novel 2-hydrazinobenzothiazole derivatives having a different structure from the above-mentioned known hydrazinobenzothiazole derivatives, and have discovered that they are compounds with excellent herbicidal activity. We have arrived at the present invention.

Thus, according to the present invention, the general formula (I)R' [where R5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a
R2 and R3 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 3 or 4 carbon atoms, or an optionally substituted aryl group. or an optionally substituted pyridinyl group.

R4, R6, R6 and R7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 2-hydrazinobenzothiazole derivatives are provided.

Furthermore, the present invention provides a herbicide characterized by containing the above compound of formula (I) as an active ingredient.

Effects of the Invention The 2-hydrazinobenzothiazole derivative represented by the above formula (I) of the present invention is a novel compound that has not been described in any literature as far as the inventors know. The 2-hydrazinobenzothiazole derivative of the present invention represented by the above formula (I) is characterized by having a di- or tri-substituted hydrazino group at the 2-position of the benzothiazole ring, and due to its structural characteristics, this It is believed that the 2-hydrazinobenzothiazole derivative of formula (I) exhibits excellent physiological activity as a herbicide.

The herbicide of the present invention has a wide herbicidal spectrum and has the excellent property of fully exhibiting its herbicidal activity with an extremely small amount of use compared to ordinary herbicides.

Detailed Description of the Invention Next, the 2hydrazinobenzothiazol derivative represented by the general formula (I) of the present invention will be described in more detail.

In the hydrazino group in the general formula (I), R1 includes (1) a hydrogen atom, and (u) an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, 1s
o-propyl, n-butyl, 1so-butyl, 5ec-
Examples include butyl, ter-butynopopentyl, structural isomers thereof, and among these, alkyl groups having 1 to 3 carbon atoms are preferred, and (ii) alkanoyl groups having 2 to 6 carbon atoms include, for example, acetyl, propionyl, butyryl. , imbutyryl, valeryl, invaleryl, hexanoyl and structural isomers thereof, and among these, an alkanoyl group having 2 to 3 carbon atoms is preferred. Among the above (1) to (ii), (1) hydrogen atom is particularly preferred as R1.

R2 and R3 are the same or different, and (i) the alkyl group having 1 to 6 carbon atoms includes, for example, methyl, ethyl, n-propyl, ls○-propyl, n-butyl, 1s
Examples include o-butyl, 5ee-butyl, ter-butyl, pentyl, and structural isomers thereof, and among these, alkyl groups having 1 to 3 carbon atoms are preferable, and (u) alkenyl groups having 2 to 4 carbon atoms are , for example, vinyl, allyl or imbutenyl; (ii) an alkynyl group having 3 or 4 carbon atoms, such as glopargyl or butynyl; (iv) an optionally substituted aryl group; Phenyl group, naphthyl group or biphenyl group, preferably phenyl group, which has 1 to 5
, preferably 1 to 3 substituents,
Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen or a trifluoromethyl group, and specific examples include phenyl, 3-
Examples include trifluoromethylphenyl or 3,4-dichlorophenyl, and (v) the optionally substituted pyridinyl group may have 1 to 5, preferably 1 to 3 substituents. Examples of the substituent include an alkyl group having I to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen or a trifluoromethyl group.

R4R5, R6 and R7 are the same or different, and in addition to (1) a hydrogen atom, (u) a halogen atom is fluorine, chlorine, bromine or iodine, and among these, fluorine or chlorine is preferred. (ij) Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-7′,
1so-propyl, n-butyl, 1so-butyl, 5e
Examples include c-butyl, ter-butyl, pentyl and structural isomers thereof, and among these, alkyl groups having 1 to 3 carbon atoms are preferable, and (iv) haloalkyl groups having 1 to 6 carbon atoms include 1 to 6 carbon atoms. Suitable are the alkyl groups of (ii) above substituted with halogens, especially fluorine or chlorine;
For example, hachloromethyl, chloroethyl, dichloroethyl,
Examples include difluoromethyl, trifluoromethyl, trifluoroethyl, etc., and among these, an alkyl group having 1 to 3 carbon atoms and having 1 to 3 halogens is preferable.
(v) As the alkoxy group having 1 to 6 carbon atoms, for example,
Examples include methoxy, ethoxy, propoquine, impropoxy, butoxy or imbutoxy, ter-butoxy, and among these, an alkoxy group having 1 to 3 carbon atoms is preferred.

The general formula (1) in the present invention may be obtained by any manufacturing method. Also, the general formula (1
) may form a salt with an agriculturally acceptable acid.

The general formula (I) can be produced, for example, by the method shown below, but the present invention is not limited to products produced by this method.

R' (II) (II[) R' CI) [Wherein, RI R2R3R4R5R6 and R7 are as defined in the general formula (I) above. Ac represents an acetyl group. ] As shown in the above reaction formula, chloroben7'-)azole (I[) and acetylhydrazine (I
The compound of general formula (I) of the present invention can be produced by reacting [[) in an organic solvent or in the absence of a solvent in the presence of a base.

The reaction is carried out using 1 to 3 molar equivalents, preferably 1 to 1.5 molar equivalents, of a base based on compound (n) at O'c or room temperature for 1 to 5 hours. Examples of the base include sodium hydroxide, potassium hydroxide, sodium hydride, and potassium hydride.

After completion of the reaction, the target compound of the present invention can be isolated by pouring the reaction mixture into water and treating it according to conventional methods such as extraction with an organic solvent, recrystallization, and column chromatography.

Next, the present invention will be explained in more detail with reference to Examples.

Example Extracted with diethyl ether and dried over anhydrous magnesium sulfate. Purified by column chromatography [eluent: ethyl acetate/hexane = 115 (volume ratio)], 2.2 g (yield 74%)
) was obtained as methyl-1-7enyl-2-(2-benzothiazolyl)hydrazine.

Compounds of the present invention shown in Table 1 below were synthesized in the same manner as in the above examples. The results are summarized in Table 1. Further, Table 2 shows the N, M, and R analysis values of the obtained compound.

1.64 g (0.01 mol) of 1-acetyl-2-methyl-2-phenylhydrazine are dissolved in DMF 50d and 0.48 g (0.01 mol) of sodium hydride are dissolved at 0°C.
added. Next, 1.69 g (0°01 mol) of 2-chlorobenzothiazole was added at 0° C. and stirred at room temperature for 2 hours. The reaction solution is poured into water, and the compound represented by the above formula (I) of the present invention has extremely high herbicidal activity, so it shows extremely excellent herbicidal activity even when used in a small amount, and is highly safe for cultivated crops. It can be a useful herbicide in agriculture.

The compounds of the present invention can effectively control various weeds growing in paddy fields and fields from the pre-emergence stage to the growing season.

For example, it is possible to control annual weeds that occur in paddy fields, such as Japanese grasshopper, Japanese cypress, Japanese cypress, Japanese azalea, Japanese cypress, and Japanese firefly, as well as perennial weeds such as Japanese grasshopper, Japanese cypress, Japanese cypress, and black snail. In addition, barnyard grass, Japanese grasshopper, Japanese grasshopper, foxtail grass, sparrow gnome, Japanese barnyard grass, knotweed, Japanese barnyard grass, Japanese barnyard grass, Japanese barnyard grass, etc., which occur in fields.
It is possible to control not only annual weeds such as American goldenrod, Japanese fir, pigweed, shepherd's purse, shepherd's lily, meadowweed, commonweed, and buckwheat, but also perennial weeds such as spiny grass, bindweed, johnson grass, and grasshopper. In particular, the compound of the present invention exhibits strong weed activity against annual widespread weeds that grow in fields, such as blueberry, purslane, Japanese fir, Japanese lily, Japanese chinensis, Japanese knotweed, Japanese knotweed, Japanese knotweed, Japanese knotweed, chickweed, shepherd's shepherd's purse, commonweed, Marpa morning glory, etc. It can effectively control weeds such as oxalis, oxalis, plantain, and other weeds.

Furthermore, the compounds of the present invention can effectively control annual and perennial weeds that occur not only in rice fields and fields, but also in agricultural lands such as orchards and mulberry gardens, and in non-agricultural lands such as lawns and ridges. .

Moreover, the compound of the present invention has high safety against cultivated crops, and is particularly useful for growing useful legumes such as rice, corn, oak, barley, and useful broad-leaved crops such as soybean and cotton. Does not cause drug damage to the extent that it becomes a problem.

When using the compound (1) of the present invention as a herbicide,
Mix with carriers or diluents, additives, auxiliaries, etc. by methods known per se to prepare formulations commonly used as agricultural chemicals, such as powders, granules, wettable powders, emulsions, water-solvents, flowables, etc. used. It can also be mixed or used in combination with other agricultural chemicals, such as fungicides, insecticides, acaricides, other herbicides, plant growth regulators, fertilizers, soil conditioners, and the like.

In particular, when used in combination with other herbicides, it is possible to not only reduce the amount of chemicals used and save labor, but also to expand the herbicidal spectrum due to the synergistic action of both herbicides, and to achieve even higher effects due to the synergistic action. .

Carriers or diluents used in formulation include:
Commonly used solid or liquid carriers may be used.

Examples of solid carriers include clays such as kaolinite group, montmorillonite group, or abatalgite group, talc, mica, waxite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, and magnesium lime. , apatite, zeolite, silicic anhydride, synthetic calcium silicate, and other inorganic substances; soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose, and other organic plant substances; coumaron resin, petroleum resin , alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, copalcum, tanmal gum, and other synthetic or natural polymeric compounds; waxes such as carnauba wax and beeswax, and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, methylnaphthalene; didioxane, tetrahydro7rane; ethers such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, Alcohols such as n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol; ether alcohols such as ethylene glycol ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether; dimethyl formamide, dimethyl sulfoxide, etc. Examples include polar solvents and water.

In addition, emulsification, dispersion, wetting, spreading, spreading, binding, disintegration adjustment, active ingredient stabilization, flowability improvement, etc. of the compound of the present invention,
Surfactants and other auxiliary agents may also be used for purposes such as rust prevention and anti-freezing.

Examples of surfactants that can be used include nonionic, anionic, cationic, and zwitterionic surfactants, but usually nonionic and/or anionic surfactants are used. is used. Suitable nonionic surfactants include, for example, compounds in which ethylene oxide is polymerized and added to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; and compounds in which ethylene oxide is polymerized and added to alkylphenols such as isooctylphenol and nonylphenol. ;Butylnaphthol,
Compounds obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as octylnaphthol; Compounds obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid; Higher aliphatic esters of polyhydric alcohols such as sorbitan; Compounds obtained by polymerization addition of ethylene oxide: Compounds obtained by block polymerization addition of ethylene oxide and propylene oxide, etc. may be mentioned.

Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; alkyl sulfonate salts such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate. arylsulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate;

Furthermore, the herbicide of the present invention may contain polymeric compounds such as casein, gelatin, albumin, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, etc., for the purpose of improving the properties of the preparation and increasing the herbicidal effect. It is also possible to use adjuvants.

The above-mentioned carriers and various auxiliary agents are used individually or in combination as appropriate depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

The active ingredient content of the compound of the present invention (D) in the various formulations thus obtained varies depending on the formulation, but is usually 0.1 to 99% by weight, preferably 1 to 99% by weight. 80% by weight is most suitable.

In the case of a powder, for example, the active ingredient compound is usually contained in an amount of 1 to 25% by weight, and the remainder is a solid carrier, a surfactant, and the like.

In the case of irrigation agents, for example, the active ingredient compound is usually 25 to 9
0%, the remainder being a solid carrier and a dispersion wetting agent,
Protective colloids, antifoaming agents, etc. may be added as necessary.

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the remainder is a solid carrier, a surfactant, and the like.

Is the active ingredient compound homogeneously mixed with the solid carrier?
Alternatively, it is fixed or adsorbed uniformly on the surface of a solid carrier, and the particle diameter is about 0°2 to 1.5+n+n.

In the case of an emulsion, for example, it usually contains 5 to 30% by weight of the active ingredient compound, this includes about 5 to 20% by weight of an emulsifier, and the remainder is a liquid carrier, and if necessary, a filler and an emulsifier. Rust inhibitors etc. are added.

In the case of flowable agents, for example, the active ingredient compound is usually
~50% by weight, in addition to 3 to 10% by weight
The remainder is water, and a protective colloid, a preservative, an antifoaming agent, etc. are added as necessary.

The 2-hydrazinobenzothiazole derivative of the present invention can be used as a herbicide as a compound of general formula (1) or in any formulation form as described above.

The herbicide of the present invention can be applied to various weeds growing in rice fields and fields from the pre-emergence stage to the growing season. The application amount is lh as the amount of the compound (active ingredient amount) represented by the general formula (I).
Approximately 0.05-5 kg per a, preferably 0.1-1
kg, and the target weed type, growth stage,
The selection can be changed as appropriate depending on the application location, application time, weather, etc.

Next, several embodiments of formulation examples using the compounds of the present invention will be shown.

Note that "parts" in the following formulation examples are based on weight.

Formulation example 1 (granules) Compound N~2 5 parts bentonite 50 parts talc
40 parts Sodium dodecylbenzenesulfonate 2 parts Sodium ligninsulfonate After thoroughly mixing 2 parts or more, add an appropriate amount of water, knead, and granulate using a granulator to obtain 100 parts of granules. Formulation Example 4 (Flowable agent).

Formulation Example 2 (Irrigation agent) Compound N9 20 parts diatomaceous earth 63 parts white carbon 15 parts Sodium dodecylbenzenesulfonate 2 parts or more were mixed and uniformly mixed and ground in a kneader to obtain 100 parts of a wettable powder. .

Formulation example 3 (emulsion) Compound number 4 30 parts xylene 55 parts cyclohexanone 10 parts calcium dodecylbenzenesulfonate 3 parts polyoxyethylene alkylaryl ether
Two or more parts were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Compound NC,,9 30 parts calcium dodenlebenzenesulfonate 2 parts antifoaming agent 1 part propylene glycol 5 parts water
59 parts or more were uniformly ground and mixed in a wet ball mill to form a flowable agent of 10 parts.
I got 0 copies.

Herbicides using the compounds of the present invention can be formulated according to the formulation examples described above.

Next, the effects of the herbicide of the present invention will be explained using test examples.

Test Example 1 (Paddy soil treatment) A plastic pot with an area of 200 co+" was filled with paddy soil mixed with an appropriate amount of chemical fertilizer, and 2 paddy rice (variety: Ni Nihonbare) that had been grown in a greenhouse and had reached the 2-leaf stage were placed in it. KK(
Two plants (one plant) were transplanted, and seeds of Japanese wildflower, Japanese azalea, Japanese cypress, and firefly were sown.

Three days after transplanting and sowing rice, each compound shown in Table 2 was prepared into a wettable powder according to Formulation Example 2, and mixed with an appropriate amount of water so that the amount of active ingredient was 0.2 kg or 0.5 kg per 1 ha. It was diluted and added dropwise with a pipette. The herbicidal effect and the degree of chemical damage were investigated 25 days after the chemical treatment according to the following criteria.

The results are shown in Table 2.

Weeding effect Asakusa rate (asakusa rate relative to untreated area) 10
0 to less than 1% 9 1% or more to lO% // 8 10%/l to 20% // 7 20% to 30% // 6 30% to 40% 5 40% to 50% // 4 50%// ~ 60%/13 60
%// ~ 70% // 2 70% ~ 80%
// l 80%/l ~ 90%/10 90
% ~ 100% Degree of chemical damage: No chemical damage ±: Slight damage 12 Minor damage: Medium damage + 1 + 2 major damage Filled with paddy soil mixed with rice, and filled with two plants (2 Nipponbare) of paddy rice (variety Nihonbare) that had been grown in a greenhouse and had reached the two-leaf stage.
This 1st plant) was transplanted, and seeds of Nohie, Azena, Konagi, and Firefly were sown. 10 days after paddy rice transplantation and sowing20
After growing in a glass greenhouse at ~25°C, each compound shown in Table 3 was prepared into an aquarium according to Formulation Example 2, diluted with an appropriate amount of water so that the active ingredient was 1 kg per 1 ha, It was added dropwise with a pipette. The herbicidal effect and the degree of chemical damage were investigated according to the standards of Test Example 1 25 days after the chemical treatment.

The results are shown in Table 3.

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [However, R^1 is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkyl group with 2 to 6 carbon atoms.
R^2 and R^3 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 3 or 4 carbon atoms, or a substituted is an optionally substituted aryl group or an optionally substituted pyridinyl group. R^4, R^5, R^6 and R^7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. is an alkoxy group] A 2-hydrazinobenzothiazole derivative represented by the following. (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [However, R^1 is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkyl group with 2 to 6 carbon atoms.
R^2 and R^3 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 3 or 4 carbon atoms, or a substituted is an optionally substituted aryl group or an optionally substituted pyridinyl group. R^4, R^5, R^6 and R^7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. An herbicide containing a 2-hydrazinobenzothiazole derivative represented by the following as an active ingredient.