JPH0377861A - Fluorine-containing sulfonamide derivative, insecticide and acaricide - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula R-SO2-NHCH2CH2F (R is 1-4C alkyl, haloalkyl, cycloalkyl, naphthyl, benzyl, thienyl, etc.). EXAMPLE:N(2-Fluoroethyl)benzenesulfonamide. USE:An insecticide and acaricide showing excellent insecticidal activity against insects pests such as leafhoppers, insects of the family Deltocephalidae and acarids harmful in terms of agriculture and horticulture and having permeating insecticidal activity. Also effective for controlling insect pests such as stinkbug, common cutworm, housefly, common gnat, German cockroach, etc. PREPARATION:A sulfonyl chloride derivative shown by the formula R-SO2-Cl is reacted with monofluoroethylamine in an aqueous solvent or non-aqueous solvent (e.g. methylene chloride) in the presence of a base (e.g. triethylamine) under cooling with ice to 50 deg.C to give a fluorine-containing sulfonamide derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a novel fluorine-containing sulfonamide derivative and an agent for controlling pests such as worms and mites containing the same as an active ingredient.

[Prior Art] Various sulfonamide derivatives have been reported as pest control agents. For example, Tokuko Sho 46-2801
Publication No. 4 discloses that chlormethanesulfonamide is useful against spider mites, and Japanese Patent Application Laid-open No. 1983-
61) No. 47, JP-A-55-38354-A, and JP-A-63-J52O5 also disclose that it is useful against mites.

Regarding fluorine-containing compounds, JP-A No. 63-227552 discloses that 2-fluoroethyl chloride represented by the general formula; is useful as a pest control agent; There is no suggestion whatsoever regarding the permeability of ethyl derivatives.

[Problems to be Solved by the Invention] The present inventors have conducted extensive research to develop a drug M that can effectively control pests in soil treatment that utilizes this osmotic transfer property, and as a result, the following general formula has been developed. It was discovered that the compound shown in CI) has high permeability, and the present invention was completed.

[Means for Solving the Problems] The present invention provides a general formula (summer) R-3o, -NHCH,CH,F (I) [in the formula,
R is a C1-C4 alkyl group, haloalkyl group, cycloalkyl group, naphthyl group, benzene (where X is hydrogen, C
1-C4 alkyl group, haloalkyl group, benzyl group,
It represents a nitro group, a thienyl group, and a cyano group, and m is 1 to
2 is shown. The present invention provides a novel fluorine-containing sulfonamide derivative represented by ) and a pest control agent containing this compound as an active ingredient.

Compound 2H) of the present invention can be produced by the following method.

[Method 1] General formula % formula % () (wherein R is the same as above 1) 1). ) and monofluoroethylamine in an aqueous or non-aqueous solvent in the presence of a base, ice-cooled to
The reaction is carried out at a reaction temperature between 0°C.

Examples of solvents include water, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, and xylene, diethyl ether,
THF, dioxane, ethers such as glymes, DM
F%DMSO etc. are removed. Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride, or triethylamine, pyridine, dimethylaminopyridine, DBU,
, DBN, and other organic bases.

[Method 2] A compound represented by the general formula % formula % () (wherein R has the same meaning as above) and a compound represented by the general formula % formula % () (wherein, X means CI, Br or I A compound represented by Suruya) is reacted in a solvent in the presence of a base at a reaction temperature between ice cooling and continuous flow. The same solvent and base as in Method 1 can be used.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (Compound 1) 9.95 g of N-2-fluoroethyl to 9-fluoroethylamine hydrochloride (
0.1 mol) was suspended in 80 d of methylene chloride, and 30.4 m (0.22 mol) of triethylamine was added. Under water cooling, benzenesulfonyl chloride 17°66 g (0,
1 mol) was dissolved in 30 m of methylene chloride and added dropwise. After the dropwise addition, the temperature was raised to room temperature and stirred for 8 hours. After the reaction, it was diluted with ethyl chloride, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and hexane was added to cause crystallization, and then the crystals were evaporated and dried. Recrystallization from ethyl acetate/low hexane yielded tho(2-fluoroethyl)benzenesulfonate (19.25 g, yield: 194.7
%) of colorless crystals were obtained.

Melting point: 97-98°C 'H-NMR (CDCl5): 63.32 (d-d-t, J=6Hz, J''5Hz, 2
H), 4.45 (d-t, J=48Hz, J-5Hz
, 2H), 5.17 (broad t, J=6Hz, I
H), 7.4-8.05 (Otori 51) Example 2 (Compound 2) 1.50 g (15 mmol) of 2-fluoroethylamine hydrochloride of this amino acid was added to N-2-fluorethyl ethane in methylene chloride. 30 s & 4.5 m (33 mmol) of triethylamine was added. Under water cooling, 1.93 g (15 mmol) of ethanesulfonyl chloride was dissolved in 20-methylene chloride and added dropwise. After raising and lowering Ws, the temperature was raised to room temperature and stirred overnight. After the reaction, it was washed with water and dried over anhydrous magnesium sulfate. The solvent was removed, and the residue was purified by silica gel chromatography (methylene chloride) to give tho(2-fluoroethyl)ethanesulfonamide (
1.48 g (yield: 80.0%) was obtained as a pale yellow viscous body.

'H-NMR (CDC13): 6 1.44 (t, J=8Hz, 3H), 3.18 (q
, J=8) 1z, 2H), 3.54(d-d-t, J=
27Hz, J=6Hz, J=5Hz, 2N>, 4.6
2 (d-t, J=49HzJ=5Hz, 2H), 5.2
6 (broad t, J=6Hz.IH) Examples 3-4
4 (Compounds 3 to 44) Compounds of formula (1) were synthesized in the same manner.

The results are shown in Tables 1 and 2.

The insecticide and acaricide of the present invention contains the above-mentioned fluorine-containing sulfonamide derivative as an active ingredient, and the present derivative alone or in combination with each of 1) auxiliary substances such as a diluent, a solvent, a surfactant, etc. It is formulated into emulsions, wettable powders, powders, fine grains, granules, etc. Examples of diluents include clay, talc, bentonite, diatomaceous earth, white carbon, and the like.

Examples of the solvent include cyclohexanone, xy1/one, toluene, methyl ethyl ketone, 2-propanol, methylnaphthalene, dimethylnaphthalene, and the like. Examples of surfactants include alkylbenzene sulfonic acid metal salts, polyoxyethylene alkylaryl ethers,
Examples include sodium alkyl sulfate, dinaphthylmethane disulfonic acid metal salt, alkylnaphthalene sulfonic acid metal salt, and lignin sulfonic acid metal salt. Other adjuvants include carboxymethyl cellulose, polyethylene glycol, gum arabic, and the like.

The blending ratio of the active ingredients is selected as necessary, but when making powders or granules, it is 0°1-・-20.
% (ill), 5-8 when using emulsion or Eiwaji
0% (by weight) is appropriate.

When using it, either spray it diluted to an appropriate concentration or apply it directly.

The insecticide and acaricide of the present invention can be used by spraying on foliage, soil, seedling box, water surface, etc.

The amount of application varies depending on the type of compound used, the target pest, the tendency of occurrence, the degree of damage, environmental conditions, the dosage form used, etc. 0.1g~IK per 10 ares
g, preferably selected from the range of 1 g to 300 g.

When used in liquid form, such as in the case of emulsions and wettable powders, the content should be appropriately selected from the range of 0.1 to 1.000 ppm, preferably 10 to 500 ppm.

The insecticide and acaricide of the present invention can also be used in combination with other insecticides and fungicides.

Next, examples of the insecticide and acaricide of the present invention will be specifically explained. % in the following examples indicates weight percentage.

Example 45 (Emulsion) 30% of Compound (1), 20% of cyclohexanone, 1% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene were uniformly dissolved to prepare an emulsion.

Implementation N46 (hydrating powder) Compound (14) 40%, diatom ±15%, clay 15%
, 25% of white carbon, 2% of sodium dinaphthylmethane disulfonate, and 3% of sodium ligninsulfonate were uniformly mixed and pulverized to prepare a wettable powder.

Example 47 (Powder) 2% of compound (28), ±5% of diatoms, and 93% of clay were uniformly mixed and ground to obtain a powder.

Example 48 (granules) Compound (33) 5%, sodium salt of lauryl alcohol sulfate 2%, sodium lignin sulfonate 5%, carboxymethyl cellulose 2% and clay 8
Mix and grind 6% uniformly. Add 20 parts by weight of water to 100 parts by weight of this mixture, knead it, and use an extrusion type granulator to
After processing into granules of 4 to 32 mesh sizes, they were dried to form granules.

Next, the effects of the insecticide and acaricide of the present invention will be explained using test examples.

Test Example 1 Soybeans planted in 10 d pots were inoculated with two-spotted spider mites at the first-leaf stage, and two days later, 10,100 % of the test compound was inoculated with 10% hydration of the test compound.
The pp solution was irrigated into 20 pots, and the number of two-spotted spider mites was counted 3 and 14 days after treatment to determine the control efficiency.The results are shown in Table 3.

Third wheat test example 2 1 Infestation with aphids Cucumber seedlings planted in square rock wool were inoculated with female cotton aphids, and after giving birth, the adults were removed. 4pp of test compound 10% hydrating agent
M solution 5- was sprinkled on rock wool, and the mortality rate of insects after 3 days was determined. The results are shown in Table 4.

-1----,j Table 4 Table 5 Test Example 3 2 lj ro ζ vs ti, snoring'' 1) Cabbage leaves were immersed in a 500 ppm solution of a 10% permanent agent in the test compound, After air drying, place in a 60cc vinyl chloride cup and release 10 3rd instar diamondback moth larvae into it.
Mortality rate was determined after 1 day. The results are shown in Table 5.

[Effects of the Invention] The fluorine-containing sulfonamide derivative of the present invention is effective against insects that are harmful to agriculture and horticulture, such as aphids, diamondback moths, Japanese planthoppers, southern yellow thrips, brown planthoppers, Japanese planthoppers, and planthoppers such as the black-bottomed planthopper, It has extremely excellent insecticidal activity against 3 types of insects, spider mites, such as orange spider mite, two-spotted spider mite, apple spider mite, and Kanzawa spider mite, as well as extremely excellent systemic insecticidal activity. Furthermore, it is also effective in controlling Hemiptera such as stink bugs, Lepidoptera such as Spodoptera, Diptera such as the house fly and Culex mosquito, Coleoptera such as the bean weevil and scarab beetles, and Orthoptera such as the German cockroach.

Claims (2)

[Claims] (1) General formula R-SO_2-NHCH_2CH_2F (I) [wherein R is an alkyl group of C_1 to C_4, a haloalkyl group,
Cycloalkyl groups, naphthyl groups, benzyl groups, pyridyl groups, thienyl groups and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (where X is hydrogen, C_1 to C_4 alkyl groups,
It represents a haloalkyl group, an alkoxy group, a nitro group, a substituted amino group and a cyano group, and m represents 1-2. ) is shown. ] A fluorine-containing sulfonamide derivative represented by. (2) General formula R-SO_2-NHCH_2CH_2F (I) [wherein R is a C_1 to C_4 alkyl group, a haloalkyl group,
Cycloalkyl groups, naphthyl groups, benzyl groups, pyridyl groups, thienyl groups and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (where X is hydrogen, C_1 to C_4 alkyl groups,
It represents a haloalkyl group, an alkoxy group, a nitro group, a substituted amino group and a cyano group, and m represents 1-2. ) is shown. ] An insecticide and acaricide characterized by containing a fluorine-containing sulfonamide derivative shown in the following as an active ingredient.