JPS58150578A - 3-amidino-benzisothiazole-1,1-dioxide, manufacture and insecticide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 5-amidino-benzisothiazole-1,1
- Dioxide, its production method and its use as a pest control agent.

5-amidino-benzisothiazole-1,1-dioxide has the following formula! = 1 (In the formula, s R1 and - each represent an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 50 carbon atoms, s R1 represents a hydrogen atom or a methyl group, or R and R3 each represent a hydrogen atom or a methyl group, or Together, the oxygen atom, sulfur atom t*, can be interrupted by an NH group and represent CH3, and
l is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms.

Halo represents an alkyl group having 11 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and is represented by t).

In this case, a halogen atom means a fluorine atom, a chlorine atom, a bromine atom or a toji element atom, especially a fluorine atom and a chlorine atom.

The alkyl, haloalkyl, alkenyl and alkoxy groups represented by R3, R8 and X may be linear or branched. Examples of such groups are among others: methyl,
Trifluoromethyl, methoxy, ethyl, ethoxy, propyl, propoxy, isopropyl, isopropoxy
n s 1-1 sec- or tert-butyl group, n-
Pentyl group and its isomers, vinyl group, 1-propenyl group, 2-7'ropenyl group, isopropenyl group, 3-butenyl group or -CM-CHx CH=CH-Cu5
A preferred alkenyl group for e R1 and 8-fold is 2-propenyl group.

Examples of alkylene chains in the case of R1 and R are: propylene, butylene, pentylene and hexylene groups, which can be interrupted once or several times, but especially once, by an oxygen atom, a sulfur atom or a -NH group. . Preferred R1
and the alkylene chain of R2 is a bentylene group, CHh C
Hz-0-CH, -CH.

-1CHs CHx S CHz-CHz- or-
CHz-CHz-NH-CHz-Cu5-.

Preferred compounds of formula I are:

In the formula, %R1 and R-value each represent an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R3 represents a hydrogen atom or a methyl group, and % or %
R1 and R2 together form a C5-C6 fullkylene chain which can be interrupted by an oxygen atom, a sulfur atom or an NH group;
CH, -CHz-CHh-, and Xl represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

Among the compounds represented by formula (■), particularly preferred 4 is:
R1 and R3 each represent an alkyl group having 1 to 4 carbon atoms or a 2-propenyl group, or R, and R
3 together - CH Snow - CH Tomi - CH Yi - CHz
CHz-1CHh CHh OCHz-CHz
-1-CHz-CHz-8CHs CHz-12H represents -CH snow-CHI-NH-CHs CHz-, Rm is a hydrogen atom, and Xl is a hydrogen atom, a halogen atom, a methyl group, a trifluoro represents a methyl group or a methoxy group; in formula 1, R1 and R3 each represent an alkyl group having 1 to 4 carbon atoms or a 2-propenyl group;
Or, R1 and R3 together form -CHz-CHs
CHh CHs CHz-1CH鵞CH* OCHz-
CHz-1-CHm CHh 8 CHs CHs-
or -CHx-CH*NH-CHs-CH*-, where b R3 represents a hydrogen atom, %Xt represents a hydrogen atom, a chlorine atom, or a methyl group, and 9 represents a methoxy group.

Further preferred compounds of formula I are:
In the formula, %RI and R3 represent a methyl group and a 2-propenyl group with an n-butyl group, respectively, and R1 and R3 together represent -CH-CHI-CM-CH*C
u Mushroom 'Ma Mehi Sevenyo -Cut CHs
OCHz CHh-, R3 represents a hydrogen atom, and s Xt represents a hydrogen atom and a chlorine atom; or in the formula, R1 and R each represent a methyl group,
represents n-butyl group or 2-propenyl group, and i9 represents R8 and R3 together and -CH5CHh CHh
CHs CHz-Makuha-C
Hz-, and R and Xl each represent a hydrogen atom.

Compounds of formula I are prepared by known methods, for example as follows: tNu.

N.H.

C2 (V) (VD In formulas I to VI, the symbols R, s, R1 and X! represent the same meanings as defined in formula I, and R/Ii
Preferred benzisothiazoles represented by the formula 0, where * is a methyl group and 1 is an ethyl group, where X1 is a hydrogen atom, a chlorine atom, Examples of such benzisothiazoles which represent a methyl or methoxy group, but in particular a hydrogen or chlorine atom, are inter alia:! &-aminobenzithiazole-1,1-dioxide: 5-aminol 4-
Chlorobenzisothiazole-1,1-dioxide;
3-amino-4-methylbenzisothiazole-1,1
-dioxide and 5-amino-4-methoxybenzisothiazole-1,1-dioxide, in preferred acetal represented by stratification, R1 and R
each m is an alkyl group having 1 to 4 carbon atoms or 2
- represents a propenyl group, or IdR8 and - together -CH5CHs CHs CL CIHm-1
C) Itomi-CHI 0-CHkura-CH, -1CHs C
HI 5-CHI-CHxt9 is-CHI CHI N
HCHHeHx-, s R1 represents a hydrogen atom, and R represents an ethyl group. Examples of such acecools are, among others, dimethylformamide-diethyl acetal and di-n-butylformamide-diethyl acetal and acetals of the formula:

The manufacturing method is carried out under normal pressure at 0 to 140°C, preferably 60 to 140°C, optionally in a solvent or diluent. Suitable solvents and diluents include, for example: ethers and etheral compounds, such as EVA, diethyl ether, diisopropyl ether, dioxane or tetrahydrochloride; aliphatic and aromatic hydrocarbons, 4IK benzene, toluene, xylene; and acetone. , methyl ethyl ketone and cyclohexanone.

The starting materials represented by I to V are known and can be prepared by methods analogous to known methods. A preferred method for producing benzinthiazole represented by a stratification is described in IA-O Tuba Patent Application No. 0055984 and Japanese Patent Application No. 48-24755.
derChemle ) 641 * 1 e 1 ?
41.

The compounds of formula I are suitable for controlling animal and plant pests.

These compounds of formula I are particularly suitable for controlling insects belonging to the following orders: Lepidoptera
Coleoptera) Coleoptera,
Homoptera Het
eroptera) s Hymenoptera (Dipterm) *
Thysanoptera, Orthoptera (
Orthopteri), Anoplura
), 8iphonaptera, Mallophaga, Thysanur
a) % Termitales (■5optera), Psocoptera, and Hymenoptera (Hymenoptera)
menoptera): and Acarina
) ticks (miles) and true Q (t tck@)
*L1IIK The compound represented by the formula l is used for insects that damage plants, especially insects that damage ornamental plants and useful plants, especially cotton, vegetables, rice, and fruit trees.
ttoralis) and heliothysviretsen X
(Heliothis virescens) K to ℃ and also in vegetable planting, such as Leptinotarsa dec
emline Marota) and green peach aphid (Myz
and in rice cultivation, for example Chilo 5uppne
s 5ans), White-throated Planthopper (Laudelpha)
x).

What should be emphasized here is that the above-mentioned compounds are effective against sweating insects, and 41 against sweating insects of the suborder Homoptera. In particular, it is extremely difficult to control nine sap insects of the Aphididae family, such as Aphis [abae] and the bean aphid (A.
phis craccivora) and green peach aphid (Myzui persicme)).

The active substance represented by the formula ■ is i9, flies such as Muses dsmestica and mosquito eggs;
and ectoparasitic mites and beetles, such as the following families: Ixodida x (Ixod
idae), Argasidae: L (Argasidae)
and DeA-IF Nishida Z (Dermanyssid
ae). Moreover, the compounds of formula I have a wide range of ovicidal and ovicidal larvicidal effects.

In addition, the compound represented by Formula 1 (1) has fungicidal properties and plant growth regulating properties; it also exhibits useful effects against ectoparasitic nematodes.

The compounds of the formula I are used in neat form or preferably with the auxiliaries customary in formulation technology and are therefore prepared in known manner, for example in concentrated emulsions, directly! IK is processed into sprayable or dilutable solutions, dilute emulsions, aqueous powders, soluble powders, powders or granules, and also capsules, for example in polymeric materials. application method,
For example, spraying, atomization, dusting, dusting, and also Fi douches, and likewise the type of composition Fi, selected depending on the intended purpose and the given environment.

The formulations, i.e. compositions containing the active ingredient of formula I and optionally solid or liquid adjuvants, are prepared in a known manner, e.g. by combining the active ingredient with a solvent, a filler such as a solid carrier, and any desired excipients. Surface active compounds (surfactants)
homogeneously mixed and/or ground.

Suitable solvents are: aromatic hydrocarbons, preferably C8-C12 fractions such as xylene mixtures or substituted naphthalenes; phthalate esters such as dibutyl or dioctyl phthalate; aliphatics such as cyclohexane or paraffins. Hydrocarbons; alcohols and glycols, and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether; ketones, such as cyclohexanone; such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide and epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

Solid carriers used for example in dusts and dispersible powders are generally natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acids can also be supplemented with highly dispersed absorbent polymers to improve their physical properties. Suitable granular adsorptive carriers are of the porous type, e.g. pumice, crushed brick,
sepiolite or bentonite; and suitable non-absorbent carriers are materials such as calcite or sand. A large number of pre-granulated inorganic or organic materials can also be used, such as in particular dolomite or ground plant debris.

A suitable surface-active compound should be added to the formula! It is a nonionic, cationic and/or anionic surfactant that has good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient represented by. "Surfactant" also means a mixture of surfactants.

Suitable anionic surfactants are both so-called water soaps and water-soluble synthetic surface-active compounds.

The soaps that can be used are alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (from 10 to 22 carbon atoms), such as those obtained from oleic acid or stearic acid, or from coconut oil or tallow, for example. Sodium or potassium salts of natural fatty acid mixtures. Fatty acid methyltaurine salts may also be mentioned.

However, so-called synthetic envelope activators are more frequently used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

Fatty sulfonates or sulfates are as a rule alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain alkyl groups having 8 to 22 carbon atoms, where 1 alkyl ” also includes the alkyl part of an acyl group, for example, riff 1
Nisulfonic acid, dodecyl sulfate, is the sodium or calcium salt of a fatty alcohol sulfate mixture made from natural fatty acids. These also include sulfuric esters of fatty alcohol/ethylene oxide adducts and salts of sulfonic acids. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and a fatty acid group having 8 to 22 carbon atoms.

Alkylaryl sulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or naphthalenesulfonic acid/formaldehyde condensation products. Corresponding phosphates are also suitable, for example the salts of the phosphoric acid esters of the adducts of p-nonylphenol with 4 to 14 mol of ethylene oxide.

Suitable nonionic surfactants are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which contain 3 to 30 glycol ether groups and (aliphatic) carbonization. It may contain 8 to 20 carbon atoms in the hydrogen group and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol.

Other suitable nonionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkyl polypropylene glycols having from 1 to 10 carbon atoms in the hyalkyl chain, which are from 10 to 250 ethylene glycol-ether groups and from 10 to 100
Contains 5 propylene glycol ether groups.

The above compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of nonionic surfactants are nonylphenol-polyethoxyethanol, castor oil polyglycol ether, polypropylene/polyethylene oxide adduct, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene lupitan trioleate, are also suitable nonionic surfactants.

The cationic surfactant preferably has 8 as an N-substituent.
Quaternary ammonium salts containing at least one alkyl group having from 22 to 22 carbon atoms, optionally halogenated lower alkyl groups, benzyl groups or lower hydroxyalkyl groups as further substituents. The iron salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, for example stearyltrimethylammonium chloride or penzyldi(2-chloroethyl)ethylammonium bromide.

Surfactants commonly used in the pharmaceutical industry are described, for example, in the following publications: - Mc Cutions Detergents and Emulsifiers Annual (Mc(:utcheo)
n's Detergents and Ernuls
ifiersAnnual)”, MC Publishers, Lingwood, New Chassis, 1
979 years.

Pest control preparations are, in principle, α1 to 9996,
Preferably it contains 1 to 95% of the compound of formula (1), 1 to 999% of a solid or liquid adjuvant, and 1 to 25% of a surfactant, preferably α1 to 25%.

Although commercial products are preferably in the form of concentrated compositions, consumers typically use dilute formulations.

The compositions may also contain other additives such as stabilizers, antifoams, viscosity modifiers, binders, adhesives and fertilizers to obtain specific effects.

The ready-to-use powder is obtained by intimately mixing the carrier and the active ingredient.

Formulation example of active ingredient represented by formula l (-1% by weight) t Irrigation agent a) b) c)
Active ingredients 25% 50% 75% Sodium lignin sulfonate 5% 5% Sodium chloride sulfate 5%-5% Highly dispersed silicic acid
5% 10% 10% Kaolin 62% 27% - If the active ingredient is mixed well with the auxiliary and the mixture is thoroughly milled in a suitable mill, a suspension of the desired concentration can be obtained by dilution with water. agent is obtained.

2. Emulsion Concentrate Active Ingredients 10 Chirunwam Cyclohexane 50 Thyxylene Mixture 50% An emulsion of the required concentration can be prepared from this concentrate by diluting with water.

V. Powder a) b)
Active ingredients 5% 8% Talc 95% - Kaolin
A 92% ready-to-use powder is obtained by mixing the active ingredient with the carrier and milling the mixture in a suitable mill.

4. Extruded granules Active ingredients 10% Sodium ligninsulfonate 2% Carboxymethyl cellulose 1%
87 - Mix and mill the active ingredient with the auxiliaries and moisten the mixture with water.

The mixture is extruded and dried in a stream of air.

5. Coated Granules Active Ingredients 3- Polyethylene Glycol 200 3% Kaolin 94% The pulverized active ingredient is uniformly applied to the kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained.

6 Suspension concentrate active ingredients 40 thiethylene glycol 10% Sodium recone sulfonate 1096 carboxymethyl cellulose 1 57-formaldehyde aqueous solution α 2 75-aqueous emulsion form 0.8% silicone oil water 52 auxiliary finely ground active ingredients When homogeneously mixed with the agent, a suspension thick liquid is obtained,
A suspension of the desired concentration is then obtained by dilution with water.

Example 1: Production of compound A1 represented by the following formula N=CH
-N(CHsh 2.69 of 3-amino-benzisothiazole-1,1-dioxide is mixed with dimethylformamide-diethyl acetal 7- and the mixture is heated to 120°C while stirring.
Keep for 125 hours. After cooling the product, it is filtered with suction r.
Wash with ether on a strainer and dry at 20°C. Compound A1 having a melting point of 233° C. is thus obtained.

The following compounds are obtained in a similar manner.

Example 2: Bean aphid (Aphia cracci)
Before the start of the contact insecticidal activity test against Vicia fabae (Vicia fabae), about 200 bean aphids were attached to each of the stingy cultivated bean plants (Vicia fabae). After 24 hours, the plants thus infected were sprayed with a solution containing 200 or 100 mg of the test compound. Mortality was further evaluated after 24 hours using two plants for each concentration and each test compound. In this test, the compound of Example 1 exerted the level of action against pea aphids as shown in Table 3.

Example 3: Systemic insecticidal action against bean aphids Rooted bean plants were transplanted into 600 ccm of soil and then treated with 50 or 12 cm of the test compound.
．． 5 - Solution containing (prepared from 25% water conservator) 50
Pour 1 directly on top.

After 24 hours, insects of the bean aphid species were placed on the parts of the plants that were above the soil, and the insects were protected from contact with the test substance or from gas action by placing a glass cylinder over each plant. . The mortality rate was evaluated 48 hours and 72 hours after the start of the test. Two plants, each planted in a separate bee, were used for a given concentration of test substance. The test was conducted at 25° C. and 7096 relative humidity.

In this test, the compound of Example 1 exerted a penetrating effect on pea aphids as shown in Table 3.

Biological Test Results The test results in the above examples are summarized in a table using the following scale to indicate the insecticidal rate: A: Active ingredient concentration 12. ! 70 to 10 in J1ml
Killing of 0chi B: Killing of 70 to 100 at an active ingredient concentration of 50
Death D: 70th to 100th death at an active ingredient concentration of 200ppm■

Claims (1)

[Scope of Claims] (1) The following formula I: (wherein R8 and - are each a C1-C5 alkyl group and a C2-C5 alkenyl group t*
I, Rs has a methyl group before the hydrogen atom, or R1 and R1 together form an alkylene chain with 5 to 6 carbon atoms that can be interrupted by an oxygen atom, a sulfur atom, or a Nu group. , te is R1 and the island together -
CH -CH5-C'H*, and Xxti
A hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, a halo alkyl group having 1 to 5 carbon atoms, and 9) representing an alkoxy group having 1 to 5 carbon atoms. 5-amidino-benzisothiazole-1,1-dioxide. (R1 and Rs each represent an alkyl group having 1 to 5 carbon atoms, 9 represents an alkenyl group having 2 to 50 carbon atoms, - represents a hydrogen atom or a methyl group, or % R1 and a bird together) to form an alkylene chain of 5 to 5 carbon atoms which can be interrupted by an oxygen atom, a sulfur atom or an NH group, or a Rt and R3
together represent -CHm OH snow -CR2-, and xI represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and 9 represents an alkoxy group having 1 to 5 carbon atoms, Claim 1 Compounds described in Section. (a) Rt and R each represent an alkyl group having 1 to 4 carbon atoms or a Fi2-propenyl group;
9tiRt and 83 together -CHt -CHl
-CH, -Cu snow-CHz-1CHz Cut-0
-Cu mushroom-CH,-. -Cu Go-CHl S CHs-Cu Yuki-Mata-
CM, -CM. -NH-Cu-Cu-Cu-, R, represents a hydrogen atom, and Xl represents a hydrogen atom, a hydrogen atom, a methyl group, a trifluoromethyl group, or a methoxy group, Claim 1 Compounds described. (41R1 and R3 each represent an alkyl group having 1 to 4 carbon atoms or a 2-propenyl group, and tiRt
and R, become - embroidery -CHz CHs-CHr-CH
l CH, -1CHl -Cufu-0-Cu snow-C
Hx -CHICHm S CHI Cu鵞- or -CH, -CH, -Nu-CHl-CHl-, Rs represents a hydrogen atom, and Xl represents a hydrogen atom, a chlorine atom, a methyl group or a methoxy group; A compound according to scope item 5. <51 Rt and RS each represent a methyl group, n-butyl group or 2-propenyl group, or Rs and R together K lk Tute CHz CHx CH鵞CHI-
CHl good tf CHI CHh 0-CH IC
5. The compound according to claim 4, wherein bRl represents a hydrogen atom and Xl represents a hydrogen atom or a chlorine atom. (6) R and R3 each represent a methyl group, n-butyl group or 2-propenyl group, or R1 and R are the same group -CH* CHI CHm CHICHm
fi Seven -CHs CHs 0
-CHt CHm t represents, and R
Claim 5, wherein 3 and X each represent a hydrogen atom
Compounds described in Section. (7) The compound according to claim 6, which is represented by the following formula: % formula %). The compound according to claim 6, which is represented by: (9) The compound according to claim 6, which is represented by the following formula: % formula %). Trout The compound according to claim 6, which is represented by the following formula: asa The following formula: % formula %)) The chemical compound according to claim 6,
” The compound according to claim 6, which is represented by the following formula: CHs N=CN (C)is)s. compound. a4 The compound according to claim 5, which is represented by the following formula: - The compound according to claim 5, which is represented by the following formula: - The compound according to claim 5, which is represented by the following formula: The compound according to claim 5, which is represented by the following formula: The compound according to claim 2, which is represented by the following formula: The compound according to claim 2, which is represented by the following formula: (wherein, Xl represents the same meaning as defined in the formula!) The compound represented by the following formula: (representing an alkyl group having 1 to 5 atoms); #- represents an alkenyl group having 2 to 5 carbon atoms; R represents a hydrogen atom; nine represents a methyl group;
Alternatively, R, and R3 together form a C5-6 alkylene chain in which the oxygen and sulfur atoms can be interrupted by a NH group, or ti, R1 and Rm together form -CH Meaning - CH 鵞 represents CHm, and XJ
A hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a halo alkyl group having 1 to 5 carbon atoms represent an alkoxy group having 1 to 5 carbon atoms. ) 5-acinobenziisothiazole-1 represented by
, 1-dioxide manufacturing method. (2) As an active ingredient, the following formula: 3 (in the formula, R and RS each represent an alkyl group having 1 to 5 carbon atoms, and 9 represents an alkenyl group having 2 to 5 carbon atoms, and Rs represents a hydrogen atom before the hydrogen atom). represents a methyl group, or s R1 and Rs together form an alkylene chain of 3 to 3 carbon atoms which can be interrupted by an oxygen atom, a sulfur atom or an NH group; -CH5C1tb represents CH*, and Xl
is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, halo represents an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; Isothiazole-1
, 1-dioxide. Plow The pest control agent according to claim 20, for applying an effective amount of the compound to animal and plant pests or to their habitats. (2) The pest control agent according to claim 21 for controlling insects and acarids.