JPS59199606A - Herbicide - Google Patents

Abstract

PURPOSE:A herbicide having immediate herbicidal effect especially on annual weeds, showing no phytotoxicity to crops such as rice plants, soybeans, etc., having improved selectivity and foliar treatment, containing an alpha,beta-unsaturated carboxylic acid amine salt as an active ingredient. CONSTITUTION:A herbicide containing an alpha,beta-unsaturated carboxylic acid amine salt shown by the formula (R<1> is 1-15C straight-chain or branched aliphatic hydrocarbon group; R<2> is H, halogen, or 1-7c hydrocarbon group; R<3> is H, or 1- 20C hydrocarbon group; R<4> is 1-20C hydrocarbon group) as an active ingredient. When it is used, the active ingredient itself is used and crops may be treated with it, or it may be processed into any preparation form such as granule, wettable powder, dust, emulsion, etc. and can be used. An amount of the active component in the herbicide is usually about 0.01-about 99wt%, preferably about 0.1- about 95wt%. The compound shown by the formula has characteristics of both hydrophilic and lipophilic nature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel herbicide containing a specific α,β-unsaturated carboxylic acid amine salt as an active ingredient.

(b) Prior art Some aliphatic carboxylic acids are known to exhibit various physiological activities; for example, sorbic acid is a bactericidal agent used in food products such as cheese, etc. (see US Pat. No. 3,139,378) and 3-dennic acid have cholesterol synthesis inhibitory activity t?:k(
Biological Journal (Biochem, J.
).

147, 531-539 (see Sada (1975)) and
FI is shown. On the other hand, Japanese Patent Publication No. 47-41005 or 'Agricultural and Biological Chemistry (Agric, Biol).

chem, Vol. 45, pp. 2769-2773 (1981), β-(N-phenyl-N-methyl)amino-α-cyanoacrylic acid ester exhibits herbicidal activity, and the Hill reaction (free It has been disclosed that it has inhibitory activity (photochemical oxygen generation reaction by chloroplasts).

(c) Purpose The present inventors focused on the physiological activity Q'F of carboxylic acids, and aimed to obtain a herbicide with excellent herbicidal activity. As a result of intensive research, it was surprisingly discovered that a specific α, β-unsaturated carboxylic acid amine salt had an excellent dividing effect on various plants, especially on young coarse leather.
Moreover, they have discovered that it exhibits extremely excellent selectivity in that it does not cause phytotoxicity to crops such as rice and soybeans, and has arrived at the present invention.

(d) Structure of the invention, that is, the present invention is a herbicide containing an α-β-unsaturated carboxylic acid amine salt represented by the following general formula (1) as an active ingredient.

It provides:

The present invention will be described and explained in more detail below.

The α,β-unsaturated carboxylic acid amine salt in the present invention (in the present invention) is represented by the general formula <r), and the α,β-unsaturated carboxylic acid amine salt is represented by the general formula
P in K,'Ii, the longest chain part or main chain has 1 to 15 carbon atoms, and l/''1, which is linear, is an aliphatic hydrocarbon group having a branch.The main chain carbon When the number is 16 or more, only low herbicidal activity can be obtained, which is not preferable.

The aliphatic hydrocarbon group used has a carbon number within a theoretically limited range, but those having a total carbon number of 1 to 25 are usually preferred because of their high herbicidal activity. Further, the aliphatic hydrocarbon group is a saturated or unsaturated hydrocarbon group having a double bond.

Examples of the straight-chain aliphatic hydrocarbon group that oxidize include a methyl group, an ethyl group, and an n-propyl group.

n-butyl group, n-pentyl group, n-hexyl group, n-
hebutyl group, n-octyl group, n~/2A, g, n
-decyl group, n-undenyl group, n-dodecyl group, n-
Alkyl groups such as tridecyl group, n-tetradecyl group, n-proRz) group, n-butenyl group,
n-pentyl group + n-hexyl group, □-to7'
; ＞I group, n-octon) and M, n −/
Examples thereof include alkenyl groups such as n-2'' group, n-decenyl-gfi, n-undecenyl-2 group, n-dodecenylde group, and hridecenyl group.

Among these straight-chain aliphatic hydrocarbon groups, saturated ones are preferred in terms of herbicidal activity, and those having 1 to 13 carbon atoms are preferred.

Furthermore, a branched aliphatic hydrocarbon group has one or more branched chains having fewer carbon atoms than the main chain, and the branched chain is an aliphatic hydrocarbon group having 1 to 7 carbon atoms. Groups are preferred. Examples of the branched chain include methyl group, ethyl group, n-propyl group, and 1so-propyl group.

n-butyl group, 1so-butyl group, tert-
Butyl group, n-pentyl group, isopentyl group, etc.
knee? Examples thereof include a k lv group, each 4-p-0-2-J group, various but-and-butyl groups, and various pen≧>l groups, among which those having 1 to 3 carbon atoms are preferred.

Such a branched aliphatic hydrocarbon group is one in which the branch is bonded as a side chain to the above-mentioned straight chain aliphatic hydrocarbon group, such as 1so-propyl group, 5ee
-butyl group, tert-butyl group, +so-octyl group, 1ao-decyl group, 18o-tetrazofur group, 2.3-bis(1so-propyl)-octyl group, 1so-butyl group, 1so-off1 Examples thereof include 1-1-2 radicals, 1-so-dodecenyl-2-reme groups, and the like.

Among these branched aliphatic hydrocarbon groups, when the main chain has 1 to 13 carbon atoms, the branch carbon number is in the range of 1 to 3, and the total carbon number is in the range of 2 to 20. is preferable because it has high herbicidal activity, and saturated is more preferable.

In addition, such a linear or branched aliphatic hydrocarbon group having a main chain of 1 to 15 carbon atoms has one or more hydrogen atoms that are substituents other than the aliphatic hydrocarbon group or
It may be substituted with a rogene atom, and examples of the substituent include a cyan group, a hydroxy group, and an amine group.

An alkoxy group having 1 to 6 carbon atoms, an alkylthio group, and an alkoxy group having 7 to 10 carbon atoms.

Phenoxy groups having 6 to 10 carbon atoms, 3 to 1 carbon atoms (M
Examples include a DII cyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy groups; examples of the alkylthio group include methylthio, ethylthio, butylthio, and the like; examples of the alicyclic hydrocarbon group include ncroprobyl, cyclopentyl, and Rirohegycyl group, methylunclohexyl group, methylunchlohexyl group, nclopentenyl group, cyclohexenyl group, methylnochlohexenyl group; examples of the aromatic hydrocarbon group include phenyl group,
Examples include tolyl group, naphthyl group, etc., and these substituents may be further substituted with a halogen atom or a cyano group.

Preferred halogen atoms are bromine, chlorine, and fluorine atoms.

Among these substituted aliphatic hydrocarbon groups, those substituted with a rogen atom, a cyano group, an alkoxy group, an alkylthio group, or a ring hydrocarbon group are preferred.

As R1 in the above formula (D), among the aliphatic hydrocarbon groups explained above, a straight chain saturated aliphatic hydrocarbon group having 2 to 12 carbon atoms is used as a deweighting agent. Unique 0 Selective 7° Herbicidal activity is high and preferred.

R2 in the general formula is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 7 carbon atoms.

This hydrocarbon group having 1 to 7 carbon atoms refers to a hydrocarbon group having 1 to 7 carbon atoms.
means an aliphatic hydrocarbon group, a ring group hydrocarbon group having 53 to 70 carbon atoms, or an aromatic hydrocarbon group having 6 to 7 carbon atoms.

The aliphatic hydrocarbon group having 1 to 7 carbon atoms is a linear or branched alkyl group such as a methyl group, an ethyl group, various propyl groups, a butyl group, a pentyl group, or a hexyl group; Alkenyl groups such as silyl groups, various pro-R groups, butyl)V groups, and penmo2) groups; or phenylmethyl groups in which these are substituted with ring groups or aromatic hydrocarbon groups.7 Cyclohexylmethyl groups. etc. In addition, the alicyclic hydrocarbon group having 3 to 7 carbon atoms is 1 such as ncloprobyl group, cyclopentyl group, cyclohexyl group,
These include methylcyclohexyl group, cyclopentenyl group, cyclohexenyl group, methylcyclohexenyl group, and the like.

These hydrocarbon groups having 1 to 7 carbon atoms may be substituted with a rogen atom, an ano group, an alkoxy group having 1 to 5 carbon atoms, or the like.

R2 is preferably a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, an alkyl group or alkenyl group having 1 to 3 carbon atoms, and a hydrogen atom is particularly preferred.

R3 in the general formula (I) K is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon groups of R3 and R4 may be the same or different. Here, the hydrocarbon group having 1 to 20 carbon atoms refers to a hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an alicyclic hydrocarbon group having 6 to 20 carbon atoms. represents an aromatic hydrocarbon group.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms is linear or branched, saturated or unsaturated,
For example, methyl group, ethyl group, various propyl groups, butyl group, pequinyl group, octyl group, decyl group, dodenyl group.

Tetradecyl group, octadecyl group, Tamagoshi IV group, various pro-j-1 groups, bec-Cyl group, Nokishi)-shi group, dodecenifrete group, etc., or these are alicyclic or aromatic hydrocarbon groups Substituted compounds include, for example, cyclohexylmethyl, cyclohexylglobil, phenylmethyl, phenylethyl, etc. Among them, those having 1 to J5 carbon atoms are preferred.

Examples of alicyclic hydrocarbon groups having 3 to 20 carbon atoms include 1/clopentyl group, nclohexyl group, and various methylcyclohexyl groups.

Examples include dimethylcyclohexyl group, diethylcyclohexyl group, cyclohexenyl group, dimethylcyclohexenyl group of each m, and among them, those having 3 to 15 carbon atoms are preferred.

Furthermore, examples of the aromatic hydrocarbon group having carbons a6 to 20 include phenyl group and various tolyl groups.

Examples include diethylphenyl group, naphthyl group, methylnaphthyl group, and the like.

Such R3. Preferred hydrocarbon groups as H4 are saturated aliphatic or alicyclic hydrocarbon groups having 1 to 15 carbon atoms, and hydrogen atoms are also preferred.

Examples of the amine salt represented by the general formula (1) include ethylamine salt, ethylamine salt, dimethylamine salt, and propylamine salt.

Examples include hegycylamine salt, octylamine salt, decylamine salt, dodenylamine salt, tetratesylamine salt, nhequinolamine salt, 2-ethylhexylamine salt, soclohexylamine salt, dicyclohexylamine salt, jetylnclohexylamine salt, and the like.

α of the present invention is represented by the general formula (1).

The β-unsaturated carboxylic acid amine salt may be in either the cis form or the trans form, or may be a mixture thereof.

α, β- represented by the general formula (T) in the present invention
, β-carboxylic acid amine salts have both hydrophilic and lipophilic properties, and the hydrophobic parameter 1M value indicating the properties is in the range of -2.5 to 2.5, Furthermore, those with K in the range of -2.0 to 2.0, especially those in the range of -1.5 to 1.5, have high herbicidal activity.
It is preferable because it has a fast-acting herbicidal effect unique to the present invention.

The RM value here is defined as follows. That is, when a substance is subjected to thin layer chromatography (the volumes of the stationary phase and mobile phase and the concentration of solute in both phases are Vs and Cs, respectively)
, Ve, Ce) 1 (and moved by dx), the transfer ratio (Rf) of the solute can be expressed by the following equation.

Using such Rf, RM is expressed by the following formula.

The method for measuring the RM value using thin layer chromatography is 1, for example, Nature, Vol. 208, 537.
(1965).

The α, β-, β-carboxylic acid amine salt of the present invention may be produced by any commonly used method.

When using the herbicide of the present invention, the active ingredient, the α,β-unsaturated norboxylic acid amine salt, may be treated, but granules, wettable powders, powders, It can also be used by processing it into any of the following formulations: emulsion, fine granules, floor powder, suspension, etc.Herbicides in these formulations include talc and bentonite.

Solid carriers such as clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, ammonium sulfate, urea; water, alcohol, dioxane.

Liquid carriers such as acetone, xylene, cyclohexane, methylnaphthalene, dimethylformamide, etc.; alkyl sulfates, alkyl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers.

The above activity can be achieved using one or more of emulsifiers, dispersants, etc., such as polyoxyethylene sorbitan monoalkylate, dicaphthylmethane disulponate, and various auxiliaries, such as carboxymethyl cellulose, gum arabic, etc. It is manufactured by mixing, dissolving, granulating, etc., by appropriately blending the ingredients. The herbicide of the present invention produced in this manner and in the form of a formulation usually contains about 0.01 to about 99% by weight, preferably about 0.1 to about 95% by weight of the α, β-, β- It is desirable to contain a carboxylic acid amine salt as an active ingredient.

When using the α, β-unsaturated carboxylic acid amine salt of the present invention or the herbicide in the form of a preparation containing the α, β-, β-carboxylic acid amine salt as an active ingredient, for example, in the form of liquid or wet particulate The formulation will usually contain one or more surfactants in an amount sufficient to readily disperse the active ingredient in water or oil. The term 1 surfactant 1 includes, of course, wetting agents 9 dispersing agents, suspending agents,
Spreading agent and emulsifying (e) effect A herbicide having the α,β-unsaturated carboxylic amine salt as an active ingredient (a) in the present invention (-1°) where the active ingredient is water-soluble and oil-soluble as described above. Because it has both soluble and soluble properties, it has an excellent herbicidal effect with both foliage treatment and soil treatment, but it has particularly excellent herbicidal effect with foliage treatment. It is a characteristic.

In addition, the herbicide of the present invention is, for example, Himedio/, Mehi7
It has excellent herbicidal effects on annual weeds such as grass, and
It is characterized by its exceptional selectivity for crops such as Oiri (C), which causes almost no harm to it.

Other advantages of the herbicide of the present invention include its active ingredients, ease of production, and safety.

(f) Examples The present invention will be further explained in Section 1 below with reference to Examples, but the present invention shall not be limited in any way by the Examples.
There is no d.

Incidentally, the RM values shown in the examples were determined by the following measurement method. That is, a thin silica gel plate (manufactured by Merck, 20 > x 20 cx, m thickness o, 25 mm
) Was treated with 1% liquid paraffin/n-hexane and measured by reverse layer chromatography.

First, an acetone solution (or aqueous solution or water-acetone mixed solution) of the compound to be measured is poured onto the thin layer plate. This thin layer plate was developed with a mixed solution of acetone/water-1:1 (volume ratio).

Or<1. The transfer ratio Rf of the compound with respect to the solvent was determined from the spot on the thin laminate developed by the method, and the RM value was calculated using the following formula (% formula %).

Furthermore, in the examples, "parts" means "parts by weight."

Examples 1 to 12 0.1 part of α,β-unsaturated norboxylic acid amine salt shown in the compound column of Table 1 was mixed with 12.5 parts of water and 12.5 parts of acetone.
In addition to the above mixed solution, 5ORPOL is added as a spreading agent.
2680 (Toho Chemical System) A mixture of 0.013 parts of Himedion, Mehishiba, and rice cultivated in advance.
For about 1.5 hours (after spraying 3 times),
Furthermore, following cultivation, a withering experiment was conducted by observing the degree of withering of each plant with the naked eye. The degree of mortality 1 to 2 weeks after the treatment is shown in Table 1vc. The degree of withering, that is, the index that expresses the degree of wilting, is 1 and 1 to 1 for a plant that is in good health, 5 for a plant that is completely wilted and dead, and 4 for the in-between state.
This is expressed using a method of dividing the data into equal parts and displaying an intermediate state, a so-called five-stage method.

Comparative Example 1 A withering experiment similar to that in Example 1 was conducted using a mixed solution prepared from 2-n-ammonium octenoate + B + rc in the same manner as in Example 1. Table 1 shows its weeding effect.
It shows.

Reference example 1 Add 5ORP to a mixed solution of 12.5 parts of water and 12.5 parts of acetone.
A blight experiment similar to that in Example 1 was conducted using a mixed solution to which 0.013 part of OL 2680 was added.

The results are also shown in Table IK.

Claims (1)

[Scope of Claims] A herbicide containing an α,β-unsaturated carboxylic acid amine salt represented by the following general formula (1) % formula % () (1) as an active ingredient.