JPH06172323A - New fluorinated cycloalkanecarboxylic acid n-sulfonylamide derivative and herbicide comprising the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new fluorinated cycloalkanecarboxylic acid N- sulfonylamide derivative, capable of manifesting excellent herbicidal effects on not only annual but also perennial weeds, having high safety for a certain kind of crop and useful as a herbicide. CONSTITUTION:This fluorinated cycloalkanecarboxylic acid N-sulfonylamide derivative of formula I [R<1> and R<2> are halogen or lower alkoxy; R<3> is lower alkyl or halogen-substituted lower alkyl; R' is H, agriculturally permissible salt or lower alkyl; (n) is 0-3], e.g. the trans-isomer of N-methylsulfonyl-1- fluoro-2-(4,6-dimethoxypyrimidinyl-2-oxy)-1-cyclohexanecarboxamide. The compound of formula I is obtained by reacting a carboxylic acid of formula II with a suitable activator in the presence of a suitable base, leading the carboxylic acid once into an active intermediate and reacting the resultant intermediate with a compound of formula III. This compound of formula I has a characteristic of a fluorinated alkanecarboxylic acid N-sulfonamide part bound through O atom to a pyrimidine ring having specific substituent groups bound to the 4- and 6-positions thereof.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorinated cycloalkanecarboxylic acid N-sulfonylamide derivative which has not been described in the literature, and a herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art JP-A-3-128632 discloses a cycloalkanecarboxylic acid having a pyrimidine ring or a triazine ring and a herbicide containing the same.

[0003]

However, the compounds described in the above-mentioned documents have many points to be improved in terms of herbicidal spectrum, dosage amount, selectivity and the like. The present inventors have conducted extensive studies to develop a compound having a wide herbicidal spectrum, a high herbicidal effect, and excellent safety against crops. As a result, a cycloalkanecarboxylic acid N- having a specific position fluorinated
A fluorinated cycloalkanecarboxylic acid N-sulfonylamide derivative having a structure in which a sulfonylamide moiety and a pyrimidine ring moiety having specific substituents bonded to the 4- and 6-positions are condensed via an oxygen atom is novel. It has been found that this compound has an excellent herbicidal effect not only on annual perennial weeds but also on perennial weeds, and has high safety against certain crops, and thus completed the present invention.

That is, the present invention has the general formula (I)

[0005]

[Chemical 3]

[In the formula, R ¹ and R ² are the same or different and each represents a halogen atom or a lower alkoxy group;
³ is a lower alkyl group or a lower alkyl group substituted with a halogen atom, R ⁴ is a hydrogen atom or an agriculturally acceptable salt thereof or a lower alkyl group, and n is 0
Indicates an integer from 1 to 3. ] A fluorinated cycloalkanecarboxylic acid N-sulfonylamide derivative represented by the following and a herbicide containing the same as an active ingredient are provided.

[0007]

The compound of the present invention has the following general formula (I):

[0008]

[Chemical 4]

[In the formula, R ¹ and R ² are the same or different and each represents a halogen atom or a lower alkoxy group;
³ is a lower alkyl group or a lower alkyl group substituted with a halogen atom, R ⁴ is a hydrogen atom or an agriculturally acceptable salt thereof, or a lower alkyl group, and n is 0
Indicates an integer from 1 to 3. ] It is a fluorinated cycloalkane carboxylic acid N-sulfonyl amide derivative represented by these.

In the general formula (I), R ¹ , R ² ,
In the definition of R ³ and R ⁴ , specific examples of each group are shown below. Halogen atom; Fluorine, chlorine, iodine, bromine, lower alkoxy group ; for example, methoxy, ethoxy, n
-Propoxy, isopropoxy group, lower alkyl group; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl group, lower alkyl group substituted with a halogen atom;
Trifluoromethyl, 2-chloroethyl, 2-fluoroethyl, 3-chloropropyl, 3-fluoropropyl group, agriculturally acceptable salts; for example, inorganic salts such as sodium, potassium, calcium, and ammonium, methylammonium, Ethyl ammonium, n-propyl ammonium, isopropyl ammonium, n-butyl ammonium and its isomers, n-pentyl ammonium and its isomers, n-hexyl ammonium and its isomers, n-heptyl ammonium and its isomers, n-octyl Ammonium and its isomers, n-
Examples thereof include nonyl ammonium and its isomers, n-decyl ammonium and its isomers, and organic amine salts such as diethyl ammonium and triethyl ammonium.

The groups not specifically shown in the above groups are selected from the above atoms and groups in any combination or in accordance with the generally known common sense. In the above general formula (I) of the present invention, particularly preferred compounds are those in which n is 0
Or 1, R ¹ and R ² are each independently a chlorine atom or a methoxy group, R ³ is a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R
⁴ is a compound which is a hydrogen atom or a methyl group.

Of course, it should be understood that the optically active form of the compound represented by the above general formula (I) is within the scope of the present invention. The compound represented by the general formula (I) of the present invention has stereoisomerism on the saturated ring, and is represented by the 1-position of the general formula (I) below.

[0013]

[Chemical 5]

A compound in which the 2-position substituent has a cis configuration based on the group is defined as a cis-form (c) or a 1-position.

[0015]

[Chemical 6]

A compound in which the 2-position substituent has a trans configuration based on the group is referred to as a trans form (t). The compounds of the present invention represented by the above general formula (I) are shown in Table 1.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

The compound of the present invention is, for example, Tetrahydrone Letters Vol. 29, No. 14, pp. 1653 to 1656 (1988) or Angewande Chemie International Edition in English No. 1
It can be produced by the method shown below with reference to the method described in Vol. 8, pp. 707-721 (1979).

[0022]

[Chemical 7]

[Wherein R ¹ , R ² , R ³ , R ⁴ and n
Has the same meaning as above. In the above reaction scheme, the compound represented by the formula (I) is obtained by reacting the carboxylic acid represented by the formula (II) in the presence of a suitable base with a suitable activator under ice-cooling or the boiling point of a solvent in a temperature range. In 1
After reacting for ~ 24 hours to lead to the active intermediate, the formula (II
It can be produced by reacting with the compound represented by I).

Examples of the solvent used in the above reaction include hydrocarbon solvents such as benzene, toluene and xylene; halogenated hydrocarbon solvents such as dichloromethane and chloroform; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4. -Ether solvents such as dioxane; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl acetate and ethyl acetate; dimethylformamide, dimethyl sulfoxide,
Aprotic polar solvents such as dimethylacetamide; acetonitrile, water and the like.

Examples of the base include organic bases such as pyridine, triethylamine and diazabicycloundecene, and examples of the activator include 2-chloro-N-methylpyri 98-iodide, dicyclohexylcarbodiimide and carbonyldiimidazole. Can be mentioned. The fluorinated cycloalkanecarboxylic acid derivative of the formula (II) used as a raw material is, for example, European Patent Publication No. 04.
It can be produced by referring to the method described in No. 68766.

In the general formula (I), a salt can be formed only when R ⁴ is a hydrogen atom. The salt is, for example, in an inert solvent such as methanol, ethanol, tetrahydrofuran or acetone at a temperature of 0 to 100 ° C,
It can be obtained by reacting an alkali metal alkoxide compound or various organic amines and then distilling off the solvent.

Next, the present invention will be described more specifically with reference to examples.

[0028]

EXAMPLES Example 1 N-methylsulfonyl 1-fluoro-2- (4,6-
Dimethoxypyrimidinyl-2-oxy) -1-cyclohe
Xanthcarboxamide trans form (Compound No. 13
Production of b); European Patent Publication No. 0468766.
1-fluoro-2-synthesized according to the method described in No.
(4,6-dimethoxypyrimidinyl-2-oxy) -1
-Trans form of cyclohexanecarboxylic acid 0.35 g
15 ml of acetonitrile solution of (1.17 mmol)
In addition, 0.45 ml of triethylamine (3.22 mmo
1) and 0.34 g (1.35 mmol) of 2-chloro-N-methylpyridinium iodide were added. 3 at 50 ° C
After stirring for 0 minutes, 0.23 g of methanesulfonamide
(2.43 mmol) and triethylamine 0.22 ml
(1.60 mmol) was added and the mixture was further stirred for 30 minutes. After the reaction solution was cooled to room temperature and stirred overnight, acetonitrile was distilled off, 5 ml of 1N base and 5 ml of diethyl ether were added, and the solution was vigorously stirred. The produced compound was filtered off and dried, and 0.16 g of the trans form of the target N-methylsulfonyl 1-fluoro-2- (4,6-dimethoxypyrimidinyl-2-oxy) -1-cyclohexanecarboxamide (yield 36.3) was obtained. %) Was obtained.

Example 2 N-methylsulfonyl 1-fluoro-2- (4-chloro)
Rho-6-methoxypyrimidinyl-2-oxy) -1-si
Clo-hexanecarboxamide trans form (compound number
Preparation of 14b) 1-Fluoro-2- (4-chloro-) synthesized according to the method described in EP-A-0468766.
Trans form of 6-methoxypyrimidinyl-2-oxy) -1-cyclohexanecarboxylic acid 0.3 g (1 mmo
1 ml) in 15 ml of acetonitrile solution, 0.38 ml (2.75 mmol) of triethylamine and 2-chloro-N-
Methylpyridinium iodide 0.29g (1.15m
mol) was added. After stirring at 50 ° C. for 30 minutes, 0.20 g (2.1 mmol) of methanesulfonamide and 0.19 ml (1.37 mmol) of triethylamine were added and the mixture was further stirred for 30 minutes. After the reaction solution was cooled to room temperature and stirred overnight, acetonitrile was distilled off and 1N was added.
5 ml of hydrochloric acid and 5 ml of diethyl ether were added, and the solution was vigorously stirred. The produced compound is separated by filtration and dried to obtain the desired N-methylsulfonyl 1-fluoro-2-
0.17 g (yield 43.5%) of trans-form of (4-chloro-6-methoxypyrimidinyl-2-oxy) -1-cyclohexanecarboxamide was obtained.

Example 3 N-methylsulfonyl 1-fluoro-2- (4,6-
Dimethoxypyrimidinyl-2-oxy) -1-cyclope
Trans-sodium salt of tantancarboxamide
Compound No. 56b) produced in the same manner as in Example 1 N-methylsulfonyl 1-fluoro-2- (4,6-dimethoxypyrimidinyl-2-oxy) -1-cyclopentanecarboxamide trans form (compound) No. 13b) 0.5 g (1.
38 mmol) in 5 ml of methanol solution 0.27 g (1.3%) of 28% sodium methoxide methanol solution
8 mmol) was added and the mixture was stirred at room temperature for a while, and then the solvent was distilled off to give N-methylsulfonyl 1-fluoro-2- (4,6-dimethoxypyrimidinyl-2-.
0.53 g (yield 100%) of the sodium salt of the trans form of (oxy) -1-cyclopentanecarboxamide was obtained.

Example 4 N-methylsulfonyl 1-fluoro-2- (4,6-
Dimethoxypyrimidinyl-2-oxy) -1-cyclope
Diethylamine salt of trans-form of tantancarboxamide
Production of (Compound No. 63b) N-methylsulfonyl 1-fluoro-2- (4,6-dimethoxypyrimidinyl-2-oxy) -1-cyclopentanecarboxamide trans form (compound) synthesized by the same method as in Example 1 No. 13b) 0.5 g (1.
(38 mmol) in 5 ml of a tetrahydrofuran solution, 0.10 g (1.38 mmol) of diethylamine was added, and after stirring at room temperature for a while, the solvent was distilled off.
N-methylsulfonyl 1-fluoro-2- (4,6-
0.59 g (yield 100%) of diethylamine salt of the trans form of dimethoxypyrimidinyl-2-oxy) -1-cyclopentanecarboxamide was obtained.

The compounds shown in Table 1 above were synthesized in the same manner as in Example 1 or 2 above. Table 2 shows the NMR data of these compounds.

[0033]

[Table 5]

When the compound of the present invention is used as a herbicide, it is mixed with a carrier or diluent, an additive, an auxiliary agent and the like by a method known per se to prepare a formulation form usually used as a pesticide, for example, a powder or granules. It is prepared and used as an agent, a wettable powder, an emulsion, an aqueous solvent, a flowable agent and the like. Other pesticides, such as fungicides, insecticides, acaricides, other herbicides,
It can be used as a mixture or in combination with a plant growth regulator, a fertilizer, a soil conditioner or the like. In particular, when used in combination with other herbicides, it not only reduces the amount of the drug used and saves labor, but it is also expected that the synergistic action of both drugs will broaden the herbicidal spectrum and further enhance the synergistic effect. .

As the carrier or diluent used for formulating the compound of the present invention alone or in combination with other herbicides, solid or liquid carriers generally used in agriculture are used.

As the solid carrier, clays represented by kaolinite group, montmorillonite group, illite group or apatargite group, talc; diatomaceous earth, magnesium lime, apatite, zeolite, zeolide, silicic anhydride, Other inorganic substances such as synthetic calcium silicate; soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch,
Vegetable organic substances such as crystalline cellulose; synthetic or natural polymer compounds such as coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, cobal gum, dammal gum; and other carnauba wax, beeswax Examples thereof include waxes such as urea and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, or white oil; toluene,
Aromatic hydrocarbons such as xylene, ethylbenzene, cumene, or methylnaphthalene; ethers such as dioxane, sometimes tetrahydrofuran; ketones such as methylethylketone, diisobutylketone, cyclohexanone, acetophenone, or isophorone; ethyl acetate,
Esters such as amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, or diethyl succinate; alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, or benzyl alcohol, ethylene glycol ethyl ether,
Examples include ether alcohols such as ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

In addition, emulsification, dispersion of the compound of the present invention,
Surfactants and other auxiliaries may be used for the purposes of wetting, spreading, binding, controlling disintegration, stabilizing active ingredients, improving fluidity, and preventing rust.

As examples of the surfactant to be used, nonionic, anionic, cationic and zwitterionic compounds may be used, but usually nonionic and / or anionic compounds are used. Ionic compounds are used.

Suitable nonionic surfactants include, for example, lauryl alcohol, stearyl alcohol,
Or a compound obtained by polymerizing addition of ethylene oxide to a higher alcohol such as oleyl alcohol; a compound obtained by polymerizing addition of ethylene oxide to an alkylphenol such as isooctylphenol or nonylphenol; a compound obtained by polymerizing addition of ethylene oxide to an alkylnaphthol such as butylnaphthol or octylnaphthol Compound;
Compounds obtained by polymerizing addition of ethylene oxide to palmitic acid or higher fatty acids such as stearic acid and oleic acid;
Examples thereof include higher fatty acid esters of polyhydric alcohols such as sorbitan, compounds obtained by polymerizing addition of ethylene oxide, and compounds obtained by block-polymerizing addition of ethylene oxide and propylene oxide.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate or oleyl alcohol sulphate amine salts; sodium dioctyl sulfosuccinate or sodium 2-ethylhexene sulphonate. Alkyl sulfonates: aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

Further, in the herbicide of the present invention, for the purpose of improving the properties of the preparation and enhancing the herbicidal effect, polymers such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and polyvinyl alcohol are used. Compounds and other auxiliary agents can be used in combination.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like. The content ratio of the compound (active ingredient) of the present invention in various dosage forms thus obtained varies depending on the dosage form.
Usually, 0.1 to 99% by weight is suitable, and especially 1 to 8
Most preferred is 0% by weight. In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 25 to 90%, and the balance is a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a defoaming agent and the like are added.

In the case of powders, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance mainly comprises solid carriers and surfactants. The active ingredient compound is either uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm. In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 60% by weight, and the content thereof is about
To 20% by weight of emulsifier, the rest is liquid carrier, and rust inhibitor is added if necessary.

In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, the dispersion wetting agent is contained in an amount of 3 to 10% by weight, and the balance is water. A protective colloid agent, an antiseptic agent, an antifoaming agent and the like are added. The pyrimidine ether derivative of the present invention can be applied as it is to the compound of general formula (I) or in any of the preparation forms as described above.

The herbicide of the present invention can be applied to the control or control of various weeds that grow in paddy fields and upland fields from the pre-emergence stage to the growing season. The amount applied is 0.001 to 5 k per ha as the amount of the compound represented by the general formula (I) (the amount of active ingredient).
It is about g, preferably about 0.01 to 1 kg, and can be appropriately selected and changed depending on the kind of the target weed, the growth stage, the application place, the application time, the weather and the like.

Next, several embodiments of formulation examples using the compound of the present invention will be shown. "Parts" in the following formulation examples are based on weight.

Formulation Example 1 (Granule) Compound No. 13b 5 parts Bentonite 40 parts Talc 52 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After thoroughly mixing the above, add an appropriate amount of water and knead. Then, it was granulated using a granulator to obtain 100 parts of granules.

Formulation Example 2 (Wettable powder) Compound No. 13b 20 parts Diatomaceous earth 60 parts White carbon 15 parts Sodium lignin sulfonate 3 parts Dialkylnaphthalene sulfonate 2 parts The above components are mixed and uniformly mixed and pulverized with a jet mill. To obtain 100 parts of wettable powder.

Formulation Example 3 (Emulsion) Compound No. 13b 30 parts Xylene 55 parts Cyclohexanone 10 parts Calcium dodecylbenzenesulfonate 3 parts Polyoxyethylene alkylaryl ether 2 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Herbicides using the compound of the present invention can be prepared according to the above-mentioned preparation examples.

[0052]

The effect of the present invention is represented by the above general formula (I),
The fluorinated cycloalkanecarboxylic acid N-sulfonamide derivative is a novel compound not described in the literature. The compound represented by the general formula (I) of the present invention has a fluorinated cycloalkanecarboxylic acid N-sulfonamide moiety and a pyrimidine ring having a specific substituent bonded to the 4- and 6-positions thereof,
It is characterized by having a structure in which it is bound via an oxygen atom, and it is considered that an excellent herbicidal action is expressed by the structural characteristics.

The compound and the herbicide of the present invention can control various weeds that grow on agricultural land from the pre-emergence stage to the growing season. For example, paddy field weeds such as Nobie, Firefly, Mizuhigai, Konagi, Azaena, Mizohabe, Kishigusa, Matsubai, Urikawa, etc., or Crabgrass, Enocorogusa, Ohishiba, Suzumenohe, Suzumetenopia, Amaranthaceae, Japanese apricot, Japanese scabbard, Japanese apricot, Japanese apricot, Japanese apricot, Japanese apricot, Japanese apricot, Japanese apricot, Japanese apricot, Japanese apricot, Japanese abalone, Japanese apricot, Japanese apricot, Japanese apricot, Japanese abalone, scabbard, Japanese apricot, sardine, sardine, It is possible to control weeds such as morning glory, morning glory, ragweed, ragweed, rapeseed, sedgeweed, sengangusa, yaemgra and buckwheat vine. Furthermore, not only paddy fields and upland fields, but also orchards, mulberry fields,
It can also be used on lawns and non-cultivated lands.

Moreover, the compound of the present invention has selectivity for certain cultivated crops, and particularly excellent selectivity for crops such as cotton, soybean and corn. Next, the herbicidal effect will be described with reference to test examples.

Test Example 1 (Treatment of Upland Field and Leaves) A square pot (30 × 30 × 12 cm) was filled with upland soil, and various crops and various weed seeds shown in Table 3 were sown in fixed amounts, and each plant was 1 It was grown in a greenhouse until the leaf stage of 0.5 to 3 leaves. The compound of the present invention shown in Table 3 was used in Formulation Example 2
A water-dispersible solution was prepared in accordance with the above procedure, and the water-diluted solution was evenly sprayed onto the foliage of each plant at a spray rate of 500 l / ha so that the amount of active ingredient shown in Table 3 was obtained. Twenty-one days after spraying the chemicals, the herbicidal effect on various weeds and the degree of phytotoxicity on various crops were determined according to the following criteria. The result is the third
Shown in the table.

[0056]

[Table 6]

[0057]

[Table 7]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Rika Higurashi 8-3-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. The following general formula (I): [In the formula, R ¹ and R ² are the same or different and each represents a halogen atom or a lower alkoxy group, and R ³ represents a lower alkyl group or a lower alkyl group substituted with a halogen atom. R ⁴ represents a hydrogen atom or an agriculturally acceptable salt thereof or a lower alkyl group, and n represents an integer of 0 to 3. ] The fluorinated cycloalkane carboxylic acid N-sulfonyl amide derivative represented by these. 2. The following general formula (I): [In the formula, R ¹ and R ² are the same or different and each represents a halogen atom or a lower alkoxy group, R ³ represents a lower alkyl group or a lower alkyl group substituted with a halogen atom, and R ⁴ represents a hydrogen atom or a lower atom thereof. It shows an agriculturally acceptable salt or a lower alkyl group, and n represents an integer of 0 to 3. ] A herbicide containing a fluorinated cycloalkanecarboxylic acid N-sulfonylamide derivative represented by the following as an active ingredient.