JPS61221170A - Trifluoromethanesulfonylamide derivative and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The derivative of formula I [A is group of formula IV (X is O or oxyimino; R1 is H or 1-3C alkyl; R2 is methyl, phenyl, etc.; R3 is H or methyl), group of formula VI (R4 is H or methyl), etc.: Y is H or methyl; n is 0 or 1]. USE:A herbicide. It is a paddy field herbicide effective to main weeds in paddy field such as barnyard grass, broadleaved weeds, etc., by the treatment before the sprouting of the weeds and having excellent safety and selectivity to paddy rice plant. It exhibits excellent herbicidal effect also to the main weeds in plowed along by the treatment before sprouting or during growth and accordingly it is useful also as a herbicide for plowed land. PREPARATION:The compound of formula V (A3 is group of formula VII) can be produced by reacting the compound of formula II with equimolar amount of trifluoromethanesulfonic acid anhydride in the presence of a solvent such as 1,2-dimethoxyethane using an acid acceptor (e.g. triethylamine, pyridine, etc.), and reacting the resultant compound of formula III (A1 is group of formula VI, etc.) with hydroxylamine.

Description

Detailed Description of the Invention <Field of Industrial Application> The present invention relates to a novel trifluoromethanesulfonylamide derivative, which has herbicidal, analgesic, and anti-inflammatory effects, particularly in rice fields, fields, orchards, etc. Can be used as a herbicide.

<Prior Art> It is known that certain trifluoromethanesulfonamide derivatives are useful as active ingredients in herbicides.

For example, 2,4-dimethyl-5-trifluoromethylsulfonylaminoacetanilide (common name Mefluidi
de ) is Qer, offen 2.406.475
Also, N-trifluoromethylsulfonylbenzamide is described in USF 3,629.332 for use as a herbicide.

<Problems to be Solved by the Invention> Conventional trifluoromethanesulfonamide derivatives generally have a broad herbicidal spectrum, but have the disadvantage of poor selectivity and phytotoxicity to crops.

The present invention provides herbicides that do not have these drawbacks.

Means for Solving the Problems> The present inventors have discovered that by condensing various rings to a benzene ring as shown in the following formula (I), a compound with a broad herbicidal spectrum and less phytotoxicity can be obtained.

or -C-(CH2), -0- group, X represents an oxygen atom or an oximino group, Y represents a hydrogen atom or a methyl group, Rt represents a hydrogen atom or an alkyl group of Cs , R2 represents a hydrogen atom, a methyl group, a phenyl group, or a phenyl group substituted with a chlorine atom, R3 and R4 represent a hydrogen atom or a methyl group, and n and p represent 0 or 1.

The compound represented by formula (1) can be produced, for example, by the following method.

NH302CF3 'L3 -0-(CH2)2-0-, -CH5-O-CHs-0
-, -(CH2)4-.

(R3, R4, Yl n+ p have the same meanings as above), i.e., a compound of formula I is reacted with an equimolar amount of trifluoromethanesulfonic anhydride in the presence of the following common medium using an acid acceptor: This gives a compound of formula (III).

Examples of acid acceptors include triethylamine, dimethylaniline, and pyridine. Examples of the solvent include 1,2-dimethoxyethane, ethyl acetate, benzene, chloroform, dichloroethane, N,N-dimethylacetamide, and N,N-dimethylformamide. This reaction can also be carried out without a solvent. The reaction temperature is preferably -15°C to 150°C, more preferably -15°C to 50°C. The reaction time varies, for example, from 30 minutes to several hours.

By reacting the compound with sodium boron hydride in the presence of methyl alcohol using an appropriate solvent, the compound of formula Aromatic compounds chloroform, carbon tetrachloride,
Hydroxylamine is added to a halogenated hydrocarbon such as perchlorine, an ether such as diethyl ether, dioxane, and tetrahydrofuran, acetone, and methylethyl compound in the presence of an appropriate solvent, preferably O'C-120.
It can be obtained in good yield by reacting at a temperature between 1 and 20 hours, preferably between 1 and 20 hours. The appropriate solvent mentioned here is the same as the above-mentioned solvent.

Next, the compound of formula 0, which is a raw material for the compound of the present invention, can be produced, for example, as follows.

ClCHSCHCOCI b, p, 73-5103mmHg 1υ-5o-yield $51% yield 87% reflux yield 74% p-173-178°C yield 62.7% yield 60% Weeding with the compound of the present invention When used as an active ingredient of a drug, the compounds of the present invention may be used alone or in combination of two or more.

When the compound of the present invention is used as a herbicide, depending on the purpose of use, it may be used as it is, or it may be mixed with agrochemical adjuvants to enhance or stabilize the effect, and may be prepared as a powder or fine powder by a method commonly used in the field of agrochemical manufacturing. tablets, granules, hydrating agents,
It can be used in the form of flowable preparations, emulsions, and the like.

These various formulations can be used directly for experimental use or diluted with water to the desired concentration.

The agrochemical auxiliary agents mentioned herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersing agents, fixing agents, and disintegrants.

Liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animals and plants. Examples include oil, fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, Merck, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, and alumina sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cationic surfactants. , nonionic surfactants, and amphoteric surfactants.

All formulations can not only be used alone, but also mixed with fungicides, insecticides, plant growth regulators, acaricides, agricultural and horticultural fungicides, soil fungicides, soil conditioners, or nematicides. It can also often be used in combination with fertilizers and other herbicides.

The content of the active ingredient compound in the herbicide and plant growth regulator of the present invention varies depending on the formulation form, application method, and other conditions. In some cases, only the active ingredient compound may be included, but usually 0.5 to 95% ( weight) preferably 2
~50% (by weight).

When weeding with the herbicide of the present invention, the amount used varies depending on the compound used and the place of application, but it is usually used in the range of 1 to 50 g, preferably 1 to 20 g, of the active ingredient per are.

<Effects of the Invention> The compound of the present invention is a paddy field herbicide with excellent selectivity and is highly safe for paddy rice by weeding major weeds in paddy fields such as Japanese grasshopper, broad-leaved weeds, cypress, and bulrush by submerging treatment before the emergence of paddy field weeds. It is.

It was also found to be useful as a herbicide for upland fields, showing extremely excellent herbicidal effects on major weeds in upland fields in pre-emergence and growth treatments.

<Examples> The present invention will be described below with reference to Examples, but the present invention is not limited only to these Examples. Synthesis examples of representative compounds are shown below.

Synthesis example 1. (Compound 16) 5 g of tetrahydro-α-naphthylamine was dissolved in 50 cc of tetrahydroform, cooled, and while maintaining the internal temperature at 1°C to 0°C, 9.6 g of trifluoromethanesulfonic acid anhydride and 4.1 g of triethylamine were dissolved. Add gradually. Thereafter, the mixture is allowed to react at room temperature for 3 hours. The reaction product was poured into ice water and the organic layer was collected. Thereafter, it is washed with water, dried with Glauber's salt, and concentrated under reduced pressure. 5. The obtained crystals are re-crystallized from ethyl acetate and n-hexane.
5 g of white crystals were obtained with a mp of 85-6°C.

Elemental analysis C1□HI2 F3Nt Calculated value as O□S1 C47, 30% H4, 33% N5.01% Actual value C47, 39% H4, 30% N5.22% Synthesis example 2,
(Compound product 18) 9.9 g of 5-aminoindan in 100 cc of chloroform
21 g of trifluoromethanesulfonic acid anhydride was gradually added while maintaining the internal temperature between 1°C and θ°C. Thereafter, 12.4 CC of triethylamine was gradually added, and the mixture was allowed to react at the same temperature for 2 hours. Pour the reactants into ice water,
Separate the organic layer. Thereafter, it is washed with water, dried with Glauber's salt, and concentrated under reduced pressure. The obtained oil was distilled under reduced pressure to obtain 11 g of a colorless oil. bp127~130℃/2mmH
g Elemental analysis C1o HIOFa Calculated value as N10281 C45, 28% H3, 80% N5.28% Actual value C45, 40% H3, 91% N5.33% Synthesis example 3
．． (Compound 9) Add 30 cc of liquid and 5 cc of water. Add 2 g of sodium boron hydride to this, and react at room temperature for 10 hours. After the reaction, it is poured into ice water and the precipitated crystals are collected in F. After drying, the crystals are recrystallized from ethyl acetate and n-hexane to obtain 1.5 g of white crystals of Compound No. 9. m, p, 132
~134℃ Elemental analysis C1゜H8゜Fa Nt Oa Calculated value as Fa C40, 40%H3, 39%N4.71% Actual value C40, 22%H3, 41%N45.8% Synthesis example 4
．． (Compound Takashi 10) Hydroxylamine hydrochloride 1.04 in 30cc of water
Add g. 1.23 g of sodium acetate is gradually added while keeping the temperature below 0°C. call here 30 cc
Add the solution dissolved in the solution dropwise. Then 2 at 20℃~25℃
React for 0 hours. After the reaction, put it into ice water and collect the precipitated crystals in a furnace. After drying, the mixture was combined with ethyl acetate and n-hexane to obtain 3.56 g of white crystals of Compound 10. m
, p, 219-220'C.

(Dec) Elemental analysis Calculated value as C1o Hs Fa N204 St C38, 71% H2, 92% N9.02% Actual value C38, 68% H3, 10% N9.21% Examples of formulations will be explained in more detail.
The types and mixing ratios of additives are not limited to these, and can be used in a wide range. Note that 1 part is the part by weight.

Example of cleaving agent 1. An emulsion is obtained by adding and dissolving 35 parts of N,N-dimethylacetamide to 1050 parts of emulsion compound No. 1, and further mixing with 15 parts of polyoxyethylene alkylphenyl ether and alkyl phenylene. To use this 0.01
Use by diluting with water to a concentration of ~1%.

Example 2 of cleaving agent. Powder A powder is obtained by adding 95 parts of clay to 205 parts of compound number and mixing and pulverizing. This is used for direct spraying.

Detachment agent example 3. Wettable powder compound No. 3,050 parts were mixed with carriers of 10 parts of diatomaceous earth and 32 parts of kaolin, and then lacryl sodium sulfate.

8 parts of a mixture of sodium chloride and sodium 2,2'-dinaphthylmethanesulfonate were mixed evenly and ground to a fine powder to obtain a wettable powder. The crystal is diluted to a concentration of 0.06 to 1% and used as a suspension.

Formulation Example: 40 grains Using an appropriate mixer, 5 parts of fine powder of Compound No. 5 was added onto 94.5 parts of silica grains (16-32 meshier) using a methanol solution of 0.5 parts of polyvinyl acetate as a binder. Granules are obtained by spreading and coating. It is sprinkled directly into the soil and rice fields.

Experimental example 1. Pre-emergence of paddy field weeds Submergence treatment A fixed amount of paddy soil was packed into a 115,000 are Wagner pot to provide a planting stock, and a fixed amount of seeds of Japanese millet, Japanese staghorn, Japanese azalea, azalea, Japanese chickweed, Japanese cypress, and bulrush were sown.

After flooding to a depth of 3 crn, a diluted solution containing the active ingredient compound of the present invention in an amount of 93.1 to 50 g per area was dropped into the flooding water. Three days later, three paddy rice seedlings (Nihonbare) at the 2.5 leaf stage were transplanted. Thirty days after the chemical treatment, the herbicidal effect and the presence or absence of chemical damage to paddy rice were investigated. The investigation was conducted based on the following criteria and the results shown in Tables 2 and 3 were obtained.

*Weeding effect index 5: Complete weeding 4: Weeding around 80% 3: 60% 2: 40% 1: 20% 0: No effect Parent chemical damage index 12 No Harm +: Slightly small 1+: Small Harm @ : Medium Damage: Severe Damage ×: Withering Table 2 Experimental Example 1. Table 3: Submergence treatment before the emergence of rice field weeds
Experimental example 1. Known Compound A Known Compound B Underwater treatment before the emergence of paddy weeds Known Compound B As seen in the results of Experimental Example 1, the compound of the present invention exhibits excellent herbicidal efficacy against annual and perennial major weeds in paddy fields after one pre-emergence treatment. Ta. Moreover, it was found to be highly safe for paddy rice.

Next, we will show an example of an experiment conducted in a field.

Experimental Example 2 A certain amount of field soil was packed into a circular plastic case with a diameter of 8crIg and a depth of 8crrI, and green foxtail and soybeans were grown.

A certain amount of cotton seeds were sown and covered with soil to a thickness of about 0.5 to 1 crn. In addition, 3 tubers of Japanese muscaria per pot were planted in the surface layer 3 crn. Immediately, the entire surface of the soil was treated with a diluted solution containing the active ingredient compound of the present invention, which was adjusted to 50 g/a of the active ingredient per area. After treatment, growth was controlled in a greenhouse, and the herbicidal effect was investigated on the 20th day. The experiment was conducted in duplicate, and the average value of each was determined. The investigation criteria were the same as in Experimental Example 1, and the results shown in Table 4 were obtained.

Table 4 Experimental Example-2 Weed pre-sprout soil treatment Known compounds A and B are the same as Experimental Example 1.

Experimental Example 3 A certain amount of field soil was packed into a circular plastic case with a diameter of 8 crn and a depth of 8 crn, and seeds of Ichibi and Onamis,
In addition, a certain amount of tubers of Japanese muscaria were sown and grown, and when they grew to the 3- to 4-leaf stage, a hydrating powder containing the active ingredient compound of the present invention was diluted to 50 g/a of the active ingredient per area. The liquid was sprayed onto the plants.

The experiment was conducted in duplicate. Twenty days after the drug treatment, an investigation was conducted using the same investigation criteria as in Experimental Example 1, and the results shown in Table 5 were obtained.

Table 5 Experimental Example-3 Weed Growth Season Stalk and Leaves Treatment Known compounds A and B are the same as in Experimental Example 1.

As is clear from the results of Experimental Examples 2 and 3, the compound of the present invention can be used as a pre-germination treatment for major weeds in fields.

It can be seen that the growth treatment exhibits an extremely excellent herbicidal effect. Furthermore, as is clear from the results of Experimental Example 2, it is not harmful to crops and is suitable as a herbicide for upland fields.

Claims (2)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, A is ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ Groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups, ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ group, -O-(C
H_2)_2-O- group, -CH_2-O-CH_2-O
- groups, -(CH_2)_4- groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, -(CH_2)_3- groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. There are ▼ groups, -O-CH_2-O- groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups or ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups , X represents an oxygen atom or an oximino group, Y represents a hydrogen atom or a methyl group, R_1 represents a hydrogen atom or a C
_1 to C_3 represent alkyl, R_2 represents a hydrogen atom, a methyl group, a phenyl group, or a phenyl group substituted with a chlorine atom, R_3 and R_4 represent a hydrogen atom or a methyl group, and n and p represent 0 or 1. Trifluoromethanesulfonylamide derivatives shown in (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, A is ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ Groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups, ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ group, -O-(C
H_2)_2-O- group, -CH_2-O-CH_2-O
- groups, -(CH_2)_4- groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, -(CH_2)_3 groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. Yes ▼ group, -O-CH_2-O- group, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ groups, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups or ▲ mathematical formulas, chemical formulas, tables, etc. and R_1 is a hydrogen atom or C_1~
C_3 represents an alkyl group, R_2 represents a hydrogen atom, a methyl group, a phenyl group, or a phenyl group substituted with a chlorine atom, R_3 and R_4 represent a hydrogen atom or a methyl group, and n and p represent 0 or 1. A herbicide characterized by containing a trifluoromethanesulfonylamide derivative represented by: as an active ingredient.