JPH0421680A - Substituted phenoxypropionamide derivative and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R is of formula II (R<1> is H, halogen or lower alkyl)]. EXAMPLE:N-(2-Pyridyl)-2-[4-{N-(6-chloro-2-quinazolinyl)-N- methylamino}phenoxy]propionamide. USE:A herbicide. Capable of surely controlling various kinds of weeds, thus safely applicable to crops such as rice, barley, wheat, corn, cotton, soybeans, ned beans, beet. PREPARATION:A reaction is made between a compound of formula III (X is halogen) and a second compound of formula IV pref. in the presence of a solvent (e.g. DMF, THF).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel substituted phenoxypropionic acid amide derivatives and herbicides containing them as active ingredients.

BACKGROUND OF THE INVENTION In the cultivation of agricultural and horticultural crops, many herbicides have come to be used for weed control, which requires a great deal of labor. However, because they cause chemical damage to crops, remain in the environment, and contaminate the environment, there is a desire to develop a drug that is reliable and safe to use in low doses.

It is reported in JP-A No. 57-46969 and JP-A-Sho 6 that propionic acid derivatives having a quinazoline group have herbicidal activity.
Although these compounds are known from Japanese Patent No. 2-286975, the compounds described in these publications are by no means satisfactory in terms of safety and selectivity for crops.

Problems to be Solved by the Invention The purpose of the present invention is to provide a novel compound that has high herbicidal activity and is highly safe for crops when used as a herbicide, and a novel herbicide containing the compound as an active ingredient. There is a particular thing.

Means for Solving the Problems The present inventors synthesized various substituted propionic acid amide derivatives and examined those suitable for the above purpose. ] substituted phenoxypropionic acid amide derivatives (hereinafter referred to as
The present inventors have discovered that the compound of the present invention) exhibits excellent selective herbicidal activity, and have completed the present invention.

The compound of the present invention can be produced by the method shown in the reaction formula below.

(In the formula, X represents a halogen atom, and R has the same meaning as above.) This reaction is preferably carried out in the presence of a solvent.

Solvents include polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, aromatic hydrocarbons such as chlorobenzene, and methyl ethyl ketone. There are ketones such as, and these can be used alone or in combination.

This reaction can preferably be carried out in the presence of a basic substance. Examples of the basic substance include inorganic bases such as sodium bicarbonate, potassium carbonate, and sodium hydroxide, and tertiary amines such as triethylamine and pyridine. It is advantageous to use an amount in excess of that of the halogenoquinasoline. Furthermore, depending on the selection of solvent and reaction temperature, this reaction can also proceed without addition of a basic substance.

This reaction can be advantageously advanced by heating, and the heating temperature is from 40°C or higher to the boiling point of the solvent used, preferably from 50 to 120°C. Although the reaction time varies depending on the setting conditions, the reaction can usually be completed in 1 to 10 hours.

The reaction product can be separated from the reaction mixture by a conventional method, and if desired, it can be purified by recrystallization, column chromatography, etc.

In addition to the method described above, the compound of the present invention can also be produced by, for example, the method shown in the following reaction formula.

(In the formula, R" represents a lower alkyl group, and R has the same meaning as above.) The substituted fenoquine propionic acid amide derivative of the present invention is a new compound. Table 1 shows representative compounds of the present invention.

Table 1: Using the compounds of the present invention as herbicides - Maximum C
Appropriate amounts of one or more of the compounds represented by I) are mixed with an inert carrier and used in the form of emulsions, wettable powders, powders, granules, etc., which are commonly used forms of agricultural chemicals. Examples of solid carriers include talc, sauce, diatomaceous earth, and bentonite, and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, cyclohexane, dimethyl formaldehyde, and mineral oil. Furthermore, surfactants, stabilizers, etc. can be added if necessary for the formulation. The emulsions and wettable powders obtained in this way can be diluted with water to a predetermined concentration to form a suspension or emulsion, and in the case of powders and granules, they can be left in the soil before or immediately after weed germination. Surface treatment or soil mixing treatment. It may also be sprayed on foliage after weed germination.

Furthermore, when the compound of the present invention is used as a herbicide, known bactericides, insecticides, acaricides, herbicides, plant growth regulators, etc. can be used in combination. In some cases, it may be appropriate to add and mix other herbicides, especially for the purpose of reducing the spraying effort or for the purpose of expanding the range of grass species that can be effectively controlled. Examples of herbicides that can be added and mixed are as follows.

2.4-dichlorophenoxyacetic acid, its salts, esters and alkylamine salts, 2-methyl-4-chlorophenoquineacetic acid, its salts and esters, d,f-2-(4-chloro-〇-tolyluoquine)propionic acid , its salts and esters, 4-cya/-26-diiodophenyl octoate 2.4-dichlorophenyl-4''-nitrophenyl ether, 2.4.6-dolichlorophninyl-4''-nitrophenyl ether, 2. 4-dichlorophenyl-3'-methquin-4-nitrophenyl ether, 3, 4-dichlorophenolic acid methyl ester, 3
-Chlorophenylidoic acid isopropinopediethylthiolhamidate-5-4-10-henzil, 4-nitrophenyl-3',5'-xylyl ether, hexahydro-IH-azepine-1-carbothioic acid-8
-ethyl, 3,4-dichloropropionanilide, 2-chloro-2
', 6°-diethyl-N-(butoxymethyl)acetanilide, 2-di-4-2'', 6''-diethyl-N-(m-propoquinethyl)acetanilide, 1-(α,α-dimethylbenzyl)-3 -p=nitrile, 2,4-bis(ethylamino)-6-methylthio-1,
3,5-) riazine, 2-ethylamino-4-isopropylamino-6methylthio-1,3,5-triazine, 2,4-bis(isopropylamino)-6-methylthio-1,3,5-)lyazine, 5-tertbutyl-3-(2,4-dichloro5-isopropoquinphenyl)-1,3,4-oxadiazolin-2-one 2,6-cyclopenzonitrinobe 2,6-dichlorothiobenzamide , 2-amino-3-chloro-1,4-naphthoquinone, 2.
4-dichlorophenyl-3''-carbomethoxy-4'
-nitrophenyl ether, N-p-chlorobenzyloxyphenyl-3,45,6-titrahydrophthalimide 2, 4-';'70 lophenyl-3' -ethoxyethoxy-4°-nitrophenyl ether N-(1 -ethylpropyl)-2,6-sinitro 3,
4-xylidine, 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-pyrazol-5-yl-p-)luenesulfonate, 4-(2,4-dichlorobenzoyl)-1,3 dimethyl- 5-(pentylmethoxy) bilafur, o,o-diisopropyl-2-(pensene sulfonamide) ethylene dithiophosphate, 3.3゛-dimethyl-4-methoxybenzophenone α-(2-naphthoxy)propionanilide, 0 -ethyl-〇-(3-methyl-6-nitrophenyl)-N-s
ec-butylphosphorothioamidate, 3-isopropyl-2,1,3-benzothiacyanone-
(4)-2,2-dioquindo and its salts, S-(2-
Methyl-1-piperidyl-carbonylmethyl)-〇,O
-Z-n-propyl dithiophosphate, S-benzyl-NN-dimethylthiocarbamate. By judiciously combining one or more of these herbicides, it is possible to provide a mixture that is effective against many grass species. be.

Effect The compound of the present invention exhibits an extremely excellent selective herbicidal action against weeds of the common family such as barnyard grass, crabgrass, and foxtail grass, and is also effective against broad-leaved crops such as soybeans, adzuki beans, beets, and cotton, as well as rice, wheat, barley, and corn. It has the characteristic that it is almost harmless to cereal crops such as. The compound of the present invention can be used in both soil treatment and foliage treatment for barnyard grass, crabgrass, etc.
Radish, even at a dose that completely kills green foxtail, etc.
It has a very wide range of applications, with no effect on broad-leaved crops such as spinach, soybeans, adzuki beans, beets, and cotton, and almost no effect on cereal crops such as rice, wheat, barley, and corn. .

In addition, the compound of the present invention has a strong herbicidal power against Novieum, which is a highly harmful grass, under paddy field conditions, and has almost no effect on rice. EXAMPLES The method for producing the compounds of the present invention will be explained in detail using synthetic examples, but the present invention is not limited to these examples only.

Note that only a portion of the infrared absorption spectrum of the compound is shown.

Synthesis Example I N-(2-pyridyl)2-[4-(N-(6chloro-2-quinazolinyl)-N-methylamine)phenoxyfupropionic acid amide (compound number N-(2-pyridyl)
2.17 g of 2-(4-methylaminophenoxy)propionic acid amide, potassium bicarbonate 2. After adding 2,00 g of 2,6-dichloroquinazoline to OOg and dimethylformamide 30rd at room temperature with stirring, the mixture was heated to 70-80°C.
The reaction continued for 3 hours. After cooling, the reaction mixture was poured into water.
Extracted with benzene. The extract was washed with water, dried over anhydrous magnesium sulfate, the solvent was collected, and the resulting residue was purified by phosphoric gel chromatography to obtain 1.80 g of the target product as a pale yellow amorphous solid.

Synthesis Example 2 N-(5-ri-4-2-pyridyl)2-[:4-(N-
(6-chloro-2-quinazolinyl)-N=methylamine)phenoxyfupropionic acid amide (compound number 2) N-(5-chloro-2-pyridyl)2-(4-methylaminophenoxy)propionic acid amide 1, 53g,
Anhydrous carbonic power') 1.70 g and acetonitrile 20-
After adding 1.00 g of 2,6-dichloroquinazoline to the mixture, the mixture was heated under reflux for 5 hours. Treatment and purification were carried out in the same manner as in Synthesis Example 1 to obtain 140 g of the desired product as pale yellow crystals.

Synthesis Example 3 N-(4-methyl-2-pyridyl>2-C4-(
N-(6-chloro-2-quinazolinyl-N~methylamino)phenoquine]propionic acid amide (compound number 2-ko4-(N-(6-chloro-2-quinazolinyl)
-N-methylamino)phenoxy]propionate ethyl ether 2.00 g, 2-amino-4-methylpyridine 0
．． To a solution of 70 g and 30 rrl of xylene was added 15 g of t-butoxy JO, and the mixture was heated under reflux for 10 hours under a stream of nitrogen gas. After cooling, 0.20 rrl of acetic acid was added and the mixture was purified by silica gel column chromatography to obtain 0.90 g of the target compound. This compound obtained by the method of Synthesis Example 1, melting point, infrared absorption spectrum and T
LC etc. matched.

Next, formulation examples of the herbicide of the present invention will be listed, but the herbicide of the present invention is not limited to these formulation examples only.
c Note that parts indicate parts by weight.

Formulation Example 1 A wettable powder is prepared by mixing and pulverizing 20 parts of the present compound NO35, 35 parts of diatomaceous earth, 40 parts of talc, 3 parts of sodium ligninsulfonate, and 2 parts of sodium dodecylbenzenesulfonate.

Formulation Example 2 3 parts of the present compound No. 3, 15 parts of bentonite, 54.5 i of talc, 0 sodium dodecylbenzenesulfonate
．． Part 5! J geninsulfonic acid sodium 2 parts, clay 25
The mixture is uniformly mixed and pulverized, water is added, and the mixture is made into granules using an extrusion granulator, dried, and sieved to form granules.

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

Test Example 1 Pre-germination treatment test A 115,000 are Wagner pot was filled with field soil (clay loam), and seeds of soybean, morning glory, corn, and rice were sown. The soil was covered with the mixed soil to a depth of 2 cm. Immediately thereafter, a predetermined amount of the wettable powder obtained according to Formulation Example 1 was weighed, and 1
It was diluted with water equivalent to 100β per 0 are and sprayed on the soil surface with a small sprayer. Controlled cultivation was carried out in a greenhouse, and three weeks after the chemical treatment, the herbicidal effect and chemical damage to soybean, corn, and rice were investigated. The survey results are shown in Table 2. The numerical values in the table indicate the herbicidal effect and the chemical damage to the test crops, and specifically represent the following meanings.

Numerical weeding effect 00% control 90% or more control 8Q% or more control 70% or more control 60% or more control 50% or more control 40% or more control 30% or more control 20% or more control 19% or less control (Same growth as Musou area) ) In all test examples, the following compound described in JP-A-62-286975 was used as a comparative compound.

Test Example 2 Post-germination treatment test A 115,000 are Hugner pot was filled with field soil (clay loam), and seeds of soybean, morning glory, maize, and rice were sown. The soil was covered to a depth of 2 cm with field soil mixed with theater cane seeds. Thereafter, it was grown in a greenhouse, and two weeks later (at the 2.0-leaf stage), a predetermined amount of the hydrating powder obtained according to Formulation Example 1 was weighed, and a spreading agent ( The mixture was diluted with water containing 5,000 times Aglar, and treated with a small sprayer to treat the leaves of the plants.

The controlled growth was carried out in a greenhouse, and three weeks after the chemical treatment, the herbicidal effect and chemical damage to the test crops were investigated based on the method of Test Example 1. The survey results are shown in Table 3. The numerical values in the table indicate the herbicidal effect and the chemical damage to crops, and have the same meaning as Test Example 1.

Test Example 3 Novie pest control test under flooded conditions 115.0
A 00 are Hugner pot was filled with paddy soil, and after plowing, 50 wildflower seeds and 20 paddy rice seeds were sown at the same time and lightly covered with soil.

On the 3rd day after sowing, the compound of the present invention was used as a wettable powder according to Formulation Example 1 and treated uniformly at a predetermined amount using a watering method of 3.0 am. On the 14th day after the chemical treatment, the herbicidal effect and the chemical damage to paddy rice were investigated. The survey results are shown in Table 4.

Table Test Example 4 Transplanted paddy rice phytotoxicity test A 115,000 are Hugner pot was filled with paddy soil, and after plowing, 50 Novie seeds were sown, and at the same time, paddy rice seedlings at the 2.5 leaf stage (variety: Konhikari) were placed in the pot. After transplanting 1 plant per plant and 2 plants per plant, reduce the water depth to 3.0.
cm. When the grasshoppers reached the 1.5-leaf stage, the compound of the present invention was made into granules according to Formulation Example 2, and the prescribed amount was applied. It was processed evenly so that

On the 14th day after the chemical treatment, the herbicidal effect and the chemical damage to paddy rice were investigated. The survey results are shown in Table 5.

Effects of the invention in Table 1 The compounds of the present invention represented by maximum [■] have high herbicidal activity that can accurately exterminate various grass weeds, and are effective against various crops, especially rice, barley, wheat,
It is a new herbicide with high selectivity and safety that can be used extremely safely on corn, cotton, soybeans, adzuki beans, beets, etc.

Claims (2)

[Claims] (1) General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [In the formula, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1
represents a hydrogen atom, a halogen atom, or a lower alkyl group] A substituted phenoxypropionic acid amide derivative represented by. (2) General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [In the formula, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1
represents a hydrogen atom, a halogen atom, or a lower alkyl group] A selective herbicide characterized by containing a substituted phenoxypropionic acid amide derivative represented by the following as an active ingredient.