JPH02275855A - Novel bipyridonium compound and herbicide comprising same compound as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R1 is group shown by formula II, formula III, etc., (R2 is H or methyl; R3 is hydroxyl, nitro, etc.; (a), (b) and (c) are 0 or positive integer (a)+(b)>=1, (a)+(b)+(c)=2 to 6; R6 is 1 to 5C alkyl, phenyl, etc.); R is 1 to 5C alkyl; when R1 is monofunctional, (m)=1 and (n)=2, when R1 is bifunctional, (m)=(n)=2, when R1 is trifunctional, (m)=3 and (n)=2, when R1 is tetrafunctional, (m)=2 and (n)=1, when R1 is hexafunctional, (m)=3 and (n)=1]. USE:A herbicide having excellent safety and a wide herbicidal spectrum. PREPARATION:A solution of R1<->Na<+>, a precursor of a compound shown by formula I in water or ethanol is passed through a column of extremely strongly acidic cation exchange resin supporting CH3-<+>N-N<+>-CH3 to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION fa) Industrial Field of Application The present invention relates to a novel bipyridinium compound and a herbicide containing it as a main active ingredient. More specifically, the present invention relates to a bipyridinium compound having a specific structure containing a specific organic compound anion as a counter ion, and a novel herbicide containing the bipyridinium compound as a main active ingredient.

(b) Prior Art Conventionally, many types of bipyridinium compounds have been developed due to their excellent herbicidal activity, some of which have been industrially produced and used as herbicides.

For example, the bipyridinium compound represented by the following general formula [I[] (wherein Y represents an anion) has a wide range of herbicidal spectrum and has excellent herbicidal power.
It is currently industrially manufactured and commercially available. Such bipyridinium compounds rapidly become non-toxic in soil and have no adverse effects on crops after their application.

However, if herbicides containing the above-mentioned compounds are used for purposes other than their original purpose as agricultural chemicals, or if they are accidentally ingested, they are dangerous compounds, so it is desirable to take measures to ensure their safety. ing.

As a countermeasure, for example, an emetic, which is a heterocyclic aromatic compound, is mixed into a bipyridinium compound-containing herbicide, which is intended to cause the herbicide to be vomited out along with the active ingredient if it is accidentally ingested (Japanese Patent Publication No. 7677/1983). ), a method of adding aromatic amines with a specific odor as a warning (see West German Patent No. 2318847), a method of coloring agricultural chemicals with dyes (Japanese Patent Laid-Open No. 59-33202)
(see Japanese Patent Publication No. 2003-1110), and a method of forming a solid complex by mixing bipyridinium compounds with compounds such as catechol and p-aminobenzoic acid that form complexes, and magnesium sulfate and sodium sulfate that form hydrates (Dutch patent). (Refer to Publication No. 6809777) have been proposed, but none of these can be said to be a fundamental solution, and safety issues still remain.

(c) Purpose of the Invention The present inventors have conducted research into substances that have excellent herbicidal activity, a broad herbicidal spectrum, and are highly safe, and as a result, they have arrived at the present invention.

(d) Structure of the Invention According to the present invention, the compound of the following general formula [I] has various properties and advantages regarding its physiological activity. For example, when we investigated the herbicidal activity, we found that a novel bipyridinium compound represented by the following general formula [ll-1], which has the highest activity and is commercially available as a conventional bipyridinium herbicide, was provided; ] A herbicide containing a novel bipyridinium compound represented by the following as a main active ingredient is provided.

The bipyridinium compound represented by the general formula [E] is a novel compound that has not been previously known.

Compared to the compound represented by the bipyridinium of the general formula [I] according to the present invention, the compound of the present invention maintains the same or higher activity.

It has an extremely strong herbicidal spectrum, especially against broad-leaved weeds and narrow-leaved weeds.

Furthermore, when examining its safety for dairy animals, a particularly remarkable difference is recognized compared to the bipyridinium salt of formula []I-1]. That is, as mentioned above, the compound of formula [ll-1] has low safety for mammals and has caused various troubles. Compounds of the general formula [E] are far safer overall, and some of them can even be classified as ordinary compounds. The above general formula [engine]
By selecting a suitable combination of R and [R1e], a bipyridinium compound is provided which is substantially safe and has a high degree of herbicidal activity. Moreover, its herbicidal activity is fast-acting, and it is extremely excellent in terms of practicality.

Therefore, according to the present invention, compared to conventional herbicides, it is superior in safety, has extremely high herbicidal activity, and has a broad and specific herbicidal spectrum, making it a practical herbicide. provided.

In the general formula [E], in order to maintain herbicidal activity and reduce toxicity, which are the objectives of the present invention, R and [R
1e] is very important.

That is, in the compound represented by -i formula [I],
The two R's may be the same or different, but from the viewpoint of ease of synthesis, it is preferable that they be the same. On the other hand, when two or more R+'s are present, they are preferably the same.

Specifically, groups suitable as R are -CH3゜-CH
Examples include 2SCH3 or -CH2CONHCH3, among which -CH3 is particularly preferred. Specific examples of R1 include (11-1 phenoxyacetic acid derivatives as shown below +2) -
(2) benzoic acid derivatives as shown below; and (4) biologically related substances H3 as shown below; naphthoxyacetic acid derivatives as shown below; α get acid derivatives as shown below.

Compounds in which R and R1 are as described above are extremely excellent herbicides because they have a strong weed-killing activity on both narrow-leaved weeds and broad-leaved weeds. Further, in the general formula [I], [Rθ]
When is monovalent, m=1. When n=2.2, m=n=1.
When the valence is trivalent, m = 3, and when n = 2. When the valence is 4, m = 2. n
=1.6 indicates m=3 and n=1.

Hereinafter, specific compounds belonging to the general formula [E] of the present invention will be illustrated, but these are for the purpose of understanding the present invention, and the present invention is not limited thereto.

0H C-0" NO□ oc-oe.

Lily (20) [H:iC"N!'NΦCH3] f21) [8
3C-〇 Four! 'HΦ -CH3ko(22) [H2O
-ΦQQΦ-CH3]! H (23) [H2O-Φ Me C)l, after preparing the co-precursor R1eNaΦ, one of this or an ethanol solution was added to a super-strongly acidic cation exchange resin supporting CH3-ΦN -Ne-CH3. The target compound [I] can be obtained by passing the solution through the column.

The structure of the target compound is confirmed by infrared absorption spectrum, nuclear magnetic resonance spectrum, and liquid chromatography.

When the compound [I] of the present invention is used as a herbicide, it can be used alone or in combination with other herbicides, and it can also be used as an additive that is commonly used in herbicide compositions. It can be used by adding and mixing. For example, as organic additives, additives such as emetics, odorants, and bittering agents are added to avoid disasters such as misuse, especially accidental ingestion, to create safer herbicidal compositions. is also possible, and may generally be preferred. Also in the present invention, the presence or absence and type of emetic agent 1 odorant, bittering agent, etc. are not particularly limited as long as the conditions of the present invention are satisfied.

However, when the emetic agent 9 odorant, bittering agent, etc. is an organic type, an alkyl aromatic type or a heterocyclic type compound, it may be used in a preferable manner.

In addition to these warning substances, additives commonly used in herbicidal compositions can also be added.

That is, surfactants such as alkyl sulfates, alkyl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylate, dinaphthylmethane disulfonate, emulsifier.

Dispersants, wetting agents, binders, fixing agents, corrosion inhibitors.

One or more stabilizers can be added.

In the herbicide of the present invention, the effective amount of the compound [I] can vary depending on the purpose, but -a is 0.0
A range of 0.01 to 1.0% by weight is suitable.

However, if the herbicide manufacturer prepares the herbicide with the assumption that it will be diluted before being used as an agricultural chemical, for example, 1.0 to 5
A high concentration range of 0% by weight is preferably used.

Since the compound [I] of the present invention is water-soluble, it can be used as a herbicide in the form of an aqueous solution, but is not limited thereto, and may be an emulsion.

It can be used in various forms such as a single tablet or a gelling agent.

(e) Effect of the invention Thus, the compound of the present invention and the herbicide containing it as an active ingredient have strong herbicidal activity against both broad-leaved weeds and narrow-leaved weeds, and its spectrum range is wide. In addition, its safety against mammals is relatively high when compared with conventionally commercially available compounds of the formula [ll-1], so it is excellent and has no particular problem in practical use. Among them, there are some compounds whose safety is at a level that belongs to ordinary compounds, and if a suitable combination of R and R1 is selected in the above general formula [I], there is no substantial safety problem and the objective is achieved. Bipyridinium compounds are provided that have high herbicidal activity.

The compound of the present invention exerts its effect within or on the plant to which it is applied. That is, the compounds of the present invention lose their effectiveness by entering the soil. Due to these characteristics, it is harmless and does not damage the environment when it enters the soil, and it does not cause chemical damage to other plants from the soil. That is, the above formula [
The compounds of [I] are mainly applied via the foliage of plants at various stages of growth.

The compound [technique] of the present invention is, for example, 1 g to 10 ares.
The metabolism of plants can be regulated with amounts of 2 Kg, more preferably 5 g to IKg, particularly preferably 10 g to 200 g.

When the purpose of using the compound of the present invention is to suppress or exterminate the growth of harmful plants, a furnace containing the compound of the present invention as it is in the form of a composition can be used in a place where beneficial plants and harmful plants coexist. It can be applied directly to plants in an amount sufficient to suppress or exterminate the growth of harmful plants.

Harmful plants are generally those that enter from the surrounding natural world and reproduce in environments created by humans, such as fields.
It can be said to be a plant that is recognized by humans as being useless or harmful in its environment. Such harmful plants are commonly referred to as weeds. Target broad-leaved weeds include, for example, various species belonging to the following families.

Family Name Compositae (Xantium)
Strumarium L,) Astragalus 5inicus L, Mangostanus L, Nigrum L, Chenopodium album L, Abutilon avic ennae G) Amarunthaceae Solanaceae Chenopodiaceae (Chenopodiaceae) In addition, various narrow-leaved weeds belonging to the following families are targeted.

(Gramineae) Cyperaceae (Gramineae) Gramineae (Digituria ciliavis RetZ,
) Cypetus rotundus L, Setaria vividis, Setaria sorghum, and various crops belonging to the following families.

(Leguminasae) Poaceae (G, Max Marrill) Maize The compound [I] of the present invention is a compound of the present invention.
'j or perennial broad-leaved weeds and MAM weeds.

if) Example Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, "1 part" means parts by weight. In addition, herbicidal activity was tested using the following method and evaluated on a 6-level scale unless otherwise specified. In other words, 0 indicates that the plant remains healthy even after the application of the active compound is almost the same as before application, 5 indicates that the entire plant has withered and died due to the application of the active compound, and 4 stages ( 1, 2, 3 and 4) were provided for evaluation.

In each Example and Comparative Example, the herbicidal activity of each compound was evaluated by the following method.

A) Preparation of spray solution A solution was prepared by adding 1 part by weight of each compound to 670 parts by weight of water, and further adding 5 parts by weight of a nonionic surfactant (trade name: Tsurupol 2680 or Alsorb R30).

b) Spraying method Separately sow plant seeds in soil using the solution spray prepared as above, cultivate for 1 to 3 weeks after germination, and use plants when the size of the plants reaches 5 to 10 cm. The active compound was sprayed on foliage in a total amount as shown in Table 1 below. Cultivation continued for 2-3 weeks without further application of sprays.

Example 1 (a) Preparation of cation exchange resin column: After washing super acidic cation exchange resin AG 50w-x8 (H type) manufactured by BIORAD with water, 20 volume parts of it was placed in a glass chromatography tube with a diameter of 15 mm. put in.

In addition, 1,1'-dimethyl-4,4'-bipyridinium dichloride (hereinafter sometimes abbreviated as PQC5!2)
A 3% aqueous solution containing 7.5 parts by weight of the solution was passed through the tube.

Thereafter, excess PQG2 was removed by water washing to obtain a resin column on which CH3-ΦN2xOe-cH3 was adsorbed.

(b) Preparation of compound represented by general formula [I]: 1.0 parts by weight of 2-methyl-4-chlorophenoxyacetic acid was added to 2 parts by weight of water.
Dissolve in a mixed solvent consisting of 5 parts by volume and 25 parts by volume of ethyl alcohol.

Add IN NaOH to the solution to the point of neutralization and then stir for 30 minutes. Thereafter, this aqueous solution was concentrated to dryness to obtain 1.0 parts by weight of white sodium 2-methyl-4-chlorophenoxyacetic acid salt. Then, this 2-methyl-4-
10 parts by weight of chlorophenoxy acid sodium salt
A total of 50 parts by volume of the effluent is collected by dissolving in parts by volume of water and flowing through a resin column prepared as described above, followed by passing through ion exchanged water.

This effluent was concentrated to 5 parts by volume and added to 200 parts by volume of acetone to obtain 1.3 parts by weight of a water-soluble green solid.

The infrared absorption spectrum of this product is 1.642 cm-
Characteristic absorption was observed at ' and 1606 cm-1.

In addition, the NMR specific absorption has a δ value [ppm] of 8.95 (
d, 4H), 8.40 (d, 4H), 7.10 (d
, 4) 1) 6.70 (s, 2H), 4.45 (S,
6H), 4.18+5,6H)2.15 (s,
4H) and was confirmed to match the structure of the target compound below.

The infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR) charts of this compound are shown in FIGS. 1 and 2, respectively.

Furthermore, when toxicity was evaluated using JCLICR 4-week-old male mice, the LD50 was over 300 m17 kg. L of paraquat dichloride at this time
D50 was 150 m17Kg.

The herbicidal activity of this compound was evaluated according to the method described above. The results are shown in Table 1 below together with other Examples and Comparative Examples.

In Table 1, 'DATJ (Days after
treatment) indicates the number of days after spraying (at the time of evaluation).

Examples 2 to 25 In the same manner as in Example 1, each compound was synthesized by changing the combination of raw materials. The results of herbicidal activity evaluation are summarized in Table 1.

In addition, as a result of toxicity evaluation, the compound of Example 6], Dso(
The mouse weighed over 560 m17 kg.

The LD50 (mouse) of the compound of Example 14 is 330 mg
/Kg.

The compound of Example 16 was LDso (mouse) at 300 ng.
/Kg.

The compound of Example 17 was LDso (mouse) at 300 ng.
/Kg.

The compound of Example 18 has an LD50 (mouse) of 570 ng.
/Kg.

The compound of Example 19 has an LD50 (mouse) of 550 ng.
/Kg.

[Brief explanation of drawings]

FIG. 1 is a chart of the infrared absorption spectrum (IR) of the novel bipyridinium compound according to the present invention, and FIG. 2 is a chart of the NMR spectrum of the novel bipyridinium compound according to the present invention.

Claims (2)

[Claims] (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] However, when [R_1] in the formula is monovalent, m = 1, n = 2, 2
When it is valent, m=n=1, when it is trivalent, m=3, n=2, when it is tetravalent, m=2, n=1, when it is hexavalent, m=3, n=1. . The two R's are the same or different alkyl groups having 1 to 5 carbon atoms, and the alkyl groups include a hydroxy group, a lower alkoxy group, a lower thioalkyl group, a lower alkylcarbonyl group, a lower alkoxycarbonyl group, a carboxy group, and a carbonylamide group. , or may be substituted with a halogen group. R_1 is any one of the following compounds (a) to (d). (a) General formula ▲ Numerical formula, chemical formula, table, etc. is an integer of , a+b≧1
, indicates a number such that a+b+c=2 to 6, however,
When a=1, b=0 and R_3=hydroxyl group, c=3, 4 or 5. ). (b) General formula ▲ Numerical formula, chemical formula, table, etc. A positive plant number, d+e≧
1, d+e+f=1 to 6. ). (c) A compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_6 represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a hydroxyphenyl group.) (d) From the group consisting of ascorbic acid, shikimic acid, indoleacetic acid, oxonic acid, N-(phosphonomethyl)glycine, dimethyldithiocarbamic acid β-D-glucose-6-phosphate, and guanosine-5'-monophosphate. A novel bipyridinium compound represented by at least one selected compound. (2) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] However, when [R_1] in the formula is monovalent, 1 = 1, n = 2, 2
When it is valent, m=n=1, when it is trivalent, m=3, n=2, when it is tetravalent, m=2, n=1, when it is hexavalent, m=3, n=1. . The two R's are the same or different alkyl groups having 1 to 5 carbon atoms, and the alkyl groups include a hydroxy group, a lower alkoxy group, a lower thioalkyl group, a lower alkylcarbonyl group, a lower alkoxycarbonyl group, a carboxy group, and a carbonylamide group. , or may be substituted with a halogen group. R_1 is any one compound of writings (a) to (d). (a) General formula ▲ Numerical formula, chemical formula, table, etc. is an integer of , a+b≧1
, a+b+c=2 to 6. however,
When a=1, b=0 and R_3=hydroxyl group, c=3, 4 or 5. ). (b) General formula ▲ Numerical formula, chemical formula, table, etc. A positive integer, d+e≧
1, d+e+f=1 to 6. ). (c) A compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_6 represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a hydroxyphenyl group.) (d) From the group consisting of ascorbic acid, shikimic acid, indoleacetic acid, oxonic acid, N-(phosphonomethyl)glycine, dimethyldithiocarbamic acid β-D-glucose-6-phosphate, and guanosine-5'-monophosphate. A herbicide whose main active ingredient is a novel bipyridinium compound represented by at least one selected compound.