Agrochemical compositions and a method for preparing them

The present invention relates to stable agrochemical compositions containing an α-unsaturated amino derivative or a salt thereof. The compositions of the invention are useful as pesticides for the control of pests and their larvae in agriculture. The present invention is also directed to a process for the preparation or composition of said .agra-chemical compositions containing an α-unsaturated amino derivative or a salt thereof. The methods are useful for stabilizing an α-unsaturated amine derivative or a salt thereof in an agrochemical composition.

α-unsaturated amino derivatives or their salts having inhibitory effect on agricultural pests and similar organisms are used as insecticides. It has been found that such amines can be mixed with other insecticides and / or fungicides to form particularly valuable agrochemical compositions (EP Patent Application No. 302389; Japanese Patent Application No. 171/1990 corresponding to it).

In addition, these compounds are of low toxicity to humans, domestic animals, fish and are true enemies of agricultural pests. For practical use, these compounds are admixed, for example, with a carrier and / or excipient to obtain a conventional solid preparation such as dust, granule, wetting powder, wetting granule, seed dressing, microgranule F, etc.

However, α-unsaturated amine derivatives and their salts in solid preparations, wherein said amines and their salts with a carrier and / or filler (e.g. mineral powder) are relatively unstable.

These compounds are gradually degraded when stored for long periods at an ambient temperature of 30 ° C. This reduces the amount of active ingredient in the preparation. In addition, when the amine is mixed with one or more agrochemically active species to achieve high efficiency over a wide range while controlling labor costs, the action and degradation of such salts is often much greater in the mixed formulation than in the individual formulation.

α-unsaturated amine derivatives and their salts are very suitable for the environment as they are relatively rapidly degraded by light. However, it is possible that the high pesticide activity of the preparation may be reduced due to the degradation of the said amines in the sunlight by spraying in rice or altitude fields.

In general, various methods for stabilizing agrochemicals have been developed (EP patent application 280289; Japanese patent application 4/1989 and 4209/1987, respectively). However, these known techniques do not solve the problems described above.

There is still a need for a stable agrochemical composition containing an α-unsaturated amino derivative or a salt thereof.

Thus, it is an object of the present invention to provide improved agrochemical compositions having high stability and long-lasting protective efficacy against pests. It is a further object of the present invention to provide agrochemical compositions comprising an α-unsaturated amino derivative or a salt thereof and at least one of several agrochemically active substances.

The present invention provides novel agrochemical compositions which include:

1) at least one α-unsaturated amino derivative having the formula:

2n

<img file="LT3247B_D0001.tif" />

./X¹ \ χ² (I) wherein one of X and X is an electron acceptor and the other is hydrogen or an electron acceptor; R¹ is a group attached through a nitrogen atom; R² is hydrogen or a group attached through carbon, nitrogen or oxygen atoms; n is unsubstituted unsubstituted or substituted with 0, 1 or 2 and the heterocyclic hydrocarbon group A is substituted or either substituted with or a group and an agrochemically acceptable salt thereof, and

2) an acid with an agrochemically acceptable carrier and its preparation.

The present invention is based on the observation that agrochemically active substances are better stabilized in agrochemical compositions containing at least an acid and an agrochemically acceptable solid carrier.

The present invention provides, in the first line, novel agrochemical compositions comprising:

1) at least one α-unsaturated amino derivative having the formula:

(II),

<img file="LT3247B_D0002.tif" />

wherein B is a substituted or unsubstituted 5- or 6-membered hydrocyclic group; and R, R and R are each independently hydrogen or a substituted or unsubstituted hydrocarbon group; and an agrochemically acceptable salt thereof, and

2) Acid with an agrochemically acceptable solid carrier and its preparation.

The present invention relates to an agrochemical composition comprising at least one α-unsaturated amino derivative of the formula (I) or a salt thereof which improves stability. In combination with compound (I), the composition may contain one or more additional agrochemically active substances.

The present invention also relates to a process for the preparation or formulation of stable agrochemical compositions comprising at least one α-unsaturated amino derivative of the formula (I) or a salt thereof, optionally mixed with one or more other agrochemically active substances.

The present invention is particularly directed to agrochemical compositions containing at least one α-unsaturated amine derivative of formula (II) or a salt thereof which improves stability. The composition of the present invention may additionally contain one or more other agrochemically active substances together with compound (II).

In formula (I) above, one of X¹ and X² is an electron acceptor and the other is hydrogen or an electron acceptor. Examples of Electron Acceptors 1 2

X and X include cyano, nitro, alkoxycarbonyl (e.g. C_x_₄ alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl); hydroxycarbonyl; C₆_₁₀ aryloxycarbonyl groups such as phenyloxycarbonyl; heterocyclyloxycarbonyl groups such as pyridyloxycarbonyl and thienyloxycarbonyl (where heteroaryl is mentioned below); C_x_₄ alkylsulfonyl groups optionally substituted with halogen and the like, such as methylsulfonyl; trifluoromethylsulfonyl and ethylsulfonyl; aminosulfonyl; di-C_x.₄ alkoxyphosphoryl, acyl groups such as diethoxyphosphoryl; C_x_₄comprising alkanoyl, optionally halogen, and the like, such as acetyl, trichloroacetyl substituted 1-3 and trifluoroacetyl; carbamoyl; C

1-4 alkylsulfonylthiocarbamoyl, such as methylsulfonylthiocarbamoyl; etc.

• 1 2

One of X and X can be halogen such as fluorine, chlorine, bromine and iodine. Also X¹ and X²together with the nitrogen atom to which they are attached may form a ring

<img file="LT3247B_D0003.tif" />

More appropriate examples are groups with the formula:

<img file="LT3247B_D0004.tif" />

including O₂N-CH =, et al.

In the above formula (I), R¹ is attached via a nitrogen atom to a group of the formula:

<img file="LT3247B_D0005.tif" />

in which R⁶ is hydrogen; alkyl (for example C₁.₆ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl and n-hexyl and the like.

t.); C₆.₁₀ aryl such as phenyl, naphthyl and lower alkyl naphthyl; aralkyl (for example C₇_₉aralkyl such as benzyl, naphthylmethyl, etc.); a heterocyclic group comprising the groups mentioned below (e.g., pyridyl, etc.); C_x.₄ acyl comprising an alkanoyl such as formyl, acetyl and propionyl; C₆.₁₀ arylcarbonyl such as benzoyl; alkoxycarbonyl (for example C_x.₄ alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl); C₆__X0 aryloxycarbonyl such as phenoxycarbonyl; heterocyclyloxycarbonyl such as furyloxycarbonyl (wherein the heterocyclic group includes the groups mentioned below); C₆__X0arylsulfonyl such as phenylsulfonyl, alkylsulfonyl (e.g. C_x_₄ alkylsulfonyl (such as methylsulfonyl); dialkoxyphosphoryl (for example, diC_x,₄ alkoxyphosphoryl such as diethoxyphosphoryl); alkoxy (for example C_x_₄ alkoxy such as methoxy and ethoxy); hydroxyl; amino; dialkylamino (e.g. di-C_x_₄ alkylamino such as dimethylamino and diethylamino); acylamino (for example C_x_₄ acylamino such as formylamino, acetylamino and propiolamino); alkoxycarbonylamino (for example C_x_₄ alkoxycarbonylamino such as methoxycarbonylamino); alkylsulfonylamino (e.g. C_x_₄ alkylsulfonylamino such as methylsulfonylamino); dialkoxyphosphorylamino (e.g., di-C_x-₄ alkoxyphosphorylamino such as diethoxyphosphorylamino); aralkoxy (for example C₇.₉ aralkoxy such as benzyloxy and other phenylalkoxyls); alkoxycarbonylalkyl (for example C_x_₄ alkoxycarbonyl-C_x_₄ alkyl such as methoxycarbonylmethyl); etc. while R⁷ is hydrogen; alkyl (for example C_x.₄alkyl such as methyl and ethyl); cycloalkyl (e.g. C₃.₆ cycloalkyl such as cyclohexyl); alkenyl (e.g. C₂_₄ alkenyl such as vinyl and allyl); cycloalkenyl (for example C₃_₆cycloalkenyl such as cyclohexenyl); alkynyl (e.g. C₂_₄ alkynyl such as ethynyl); and so on.

i.e. wherein alkyl, cycloalkyl, cycloalkenyl and alkynyl may be substituted with 1 to 3 substituents selected from hydroxy, C₄_₄ alkoxy such as methoxy and ethoxy, di-alkylamino such as dimethylamino, C₄_₄ alkylthio such as isopropylthio, acylamino such as acetylamino, C_r_₄ alkylsulfonylamino such as methylsulfonylamino, tri-C 1-4 alkylsilyl such as trimethylsilyl, pyridyl or thiazolyl which may be substituted with 1-3 halogens, or R and R together with the nitrogen atom to which they are attached may form a 5 or β-membered cyclic an amino group such as

<img file="LT3247B_D0006.tif" />

Preferred examples of the R group attached via a nitrogen atom include an amino group optionally substituted with alkyl, aryl, aralkyl, heterocyclyl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclylcarbonyl, arylsulfonyl, dialkoxyphosphoryl, cycloalkyl, alkenyl, cycloalkenyl, or alkynyl;⁶ and R⁷ (for example, a disubstituted amine such as di-C₁.₆ alkylamine and NC₁.₆-alkyl-Nformylamine; a monosubstituted amine such as mono-C 1-4 alkylamine; and unsubstituted amine); a hydrazine group optionally substituted with alkyl, aryl, acyl, alkoxycarbonyl, alkylsulfonyl, dialkoxyphosphoryl or the like as defined for R; a hydroxyamine group optionally substituted with alkyl or the like as described for R.

Particularly good at Rs¹ an example is a group with the formula:

^ R⁷ in which R⁶ and R⁷ has the above meanings.

R is hydrogen or a group attached through a carbon, nitrogen or oxygen atom.

Examples of R groups attached via carbon include acyl (including alkanoyl) such as formyl, acetyl and propionyl; alkyl (e.g. Cg_₄ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, fluorobutyl, etc.); alkenyl (for example C₂_₄ alkenyl such as vinyl and alkyl); cycloalkyl (e.g. C₃.₆cycloalkyl such as cyclopentyl and cyclohexyl); C₆_₁₀ aryl such as phenyl, etc .; aralkyl (for example C₇_₉ aralkyl such as benzyl, etc.), a heterocyclic group attached through a carbon atom containing the groups mentioned below (e.g., 3- or 4-pyridyl, etc.); and the like. These groups may have 1-3 substituent groups, which may be the same or different. Examples of such substituent groups include C_&gt;4 alkylthio such as methylthio and ethylthio; C₇.₄ alkoxy such as methoxy and ethoxy; mono- or di-C₁_₄ alkylamine such as methylamine and dimethylamine; Cg_₄ alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl; C₄.₄ alkylsulfonyl such as methylsulfonyl and ethylsulfonyl; halogen such as fluorine, chlorine, bromine and iodine; C₁.₄acyl (including alkanoyl) such as acetyl; benzoyl; phenylsulfonyl; pyridyl and so on

R² examples of groups bonded through a nitrogen atom include those described for R¹.

R² examples of groups bonded through an oxygen atom include alkoxy (e.g., Ο₇.₄ alkoxy such as methoxy and ethoxy); cycloalkyloxy (for example C₃.₆ cycloalkyloxy such as cyclohexyloxy); alkenyloxy (for example C₂_₄ alkenyloxy such as vinyloxy and allyloxy); cycloalkenyloxy (for example C₃_₆ cycloalkenyloxy such as cyclohexenyloxy); alkynyloxy (for example C₂&lt;alkynyloxy such as ethynyloxy); C₆_₁₀ aryloxy such as phenyloxy and naphthyloxy; heterocyclyloxy wherein the heterocyclic group includes the hydroxy group mentioned below (e.g. thienyloxy, etc.). These groups may have 1 to 3 substituents which may be the same or different. Examples of such substituent groups include halogens such as fluorine, chlorine, bromine, phenyl etc

. . 2

The best R groups are attached via a carbon, nitrogen or oxygen atom and include formyl; alkyl (for example C_x_₄ alkyl such as methyl and ethyl) optionally substituted with alkylthio, C₁.₄ alkoxy, mono- or di-C₁.₄ alkylamine, C_T_₄ alkoxycarbonyl, C_&gt;4alkylsulfonyl, halogens such as fluorine and chlorine, acetyl, benzoyl, phenylsulfonyl, pyridyl or the like, as defined above; an optionally substituted amine (e.g., an optionally substituted amine as defined in R¹); hydroxyl optionally substituted with C_x.₄ alkyl, C₃_₆ cycloalkyl, C₂_₄ alkenyl, C₃.₆cycloalkenyl, C₂_₄ alkynyl, C₆_₁₀ aryl, heterocyclyl, or the like (e.g._b4 alkoxyl such as methoxy and ethoxy); and the like.

n is 0, 1 or 2.

-C_n-H_2n - the group in formula (I) represents a single bond, CH₂-CH₂CH₂- or

Cl!

- .CH with preference for single bond or -CH2-.

A is a heterocyclic group (e.g., a heterocyclic group optionally substituted with 1 to 3 substituents described below, in particular (I), (IV), (VIII), (XVII), (XLVI) or (XLVIII)).

Examples of Group A include 3-pyridyl, 6-chloro-3-pyridyl, 6-methoxy-3-pyridyl, 6-methyl-3-pyridyl, 6bromo-3-pyridyl, 6-fluoro-3-pyridyl, 2-chloro- 5-thiazolyl, 4-pyridyl, 2-pyridyl, 2-thiazolyl, 4-thiazolyl, 3-quinolyl and the like.

A is also a cyclic hydrocarbon group (for example, a cyclic hydrocarbon group optionally substituted with 1 or 2 substituents as described below, in particular substituent (XVII)).

Examples of such groups include C₃_₆ cycloalkyl such as cyclopropyl, cyclohexyl and phenyl, pchlorophenyl and the like.

Preferred examples of heterocyclic group A are optionally substituted pyridyl or thiazolyl such as 3-pyridyl, 4-pyridyl, 6-chloro-3-pyridyl, 6bromo-3-pyridyl, 6-fluoro-3-pyridyl and 2-chloro-5-thiazolyl.

Preferred examples of the cyclic hydrocarbon group A are halophenyl such as p-chlorophenyl.

X¹, X², R¹, R², R⁶ and A alkyl, cycloalkyl, alkentyl, cycloalkenyl, alkynyl, aryl, aralkyl, heterocyclyl and cyclic hydrocarbon groups include the groups mentioned below, optionally substituted with 1 to 5 substituents (I) to (VII) as listed below.

u

Preferably, the alkyl group has 1 to about 20 carbon atoms, more preferably 1-8 carbon atoms. The alkyl group may be straight or branched.

Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, petradecyl, tetradecyl, , cyclodecil and the like.

Preferably, the cycloalkyl group has 3 to about 6 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The alkenyl group, which may be straight or branched, has 2 to about 6 carbon atoms and includes, for example, vinyl, allyl, isopropenyl, methoxyl, 1,1-dimethylallyl, 2-butenyl, 2-pentenyl, 4-pentenyl, 5hexenyl, and similar.

A cycloalkenyl group which may be branched, preferably having from 3 to about 6 carbon atoms, includes, for example, 1-cyclopropenyl, 2-cyclopropenyl, 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 3cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl ,

1,3-cyclohexadien-1-yl, 1,4-cyclohexadien-1-yl,

1,3-cyclopentadien-1-yl, 2,4-cyclopentadien-1-yl and the like.

The alkyl group, which may be straight or branched, preferably has 2 to about 6 carbon atoms and includes, for example, ethynyl, propargyl, 2-butyn-1-yl, 3-butin-1-yl, 3-butyn-2-yl , l-butin-3-yl, 3-pentin-l-yl, 4-pentin-2-yl, 3-hexin-1-yl and the like.

The aryl group includes, for example, phenyl, naphthyl and the like.

The aralkyl group includes, for example, benzyl, phenethyl, naphthylmethyl and the like.

5- (1,2,4-thiadiazolyl), 5- (1,2,3-thiadiazolyl),

A heterocyclic group is a cyclic group having only the same heteroatoms or a cyclic group having two or more different heteroatoms, for example a heterocyclic group having a simple or fused ring with 5-8 members in each ring and having 1-5 heteroatoms independently selected from oxygen, nitrogen or sulfur. Examples of heterocyclic groups include 2- or 3-thienyl, 2- or 3furyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4 - or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3- or 5- (1,2,4-oxadiazolyl),

1.3.4- oxadiazolyl, 3- or

1.3.4- thiadiazolyl, 4- or

1.2.5- thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, 2-, 3- or 4-pyridyl N-oxide, 2-, 4- or 5- pyrimidinyl, 2-, 4- or 5-pyrimidinyl oxide, 3- or 4-pyridazinyl, 3- or 4-pyridazinyl oxide, benzofuryl, benzothiazolyl, triazinyl, oxotriazine, tetrazole (1,5-b) pyridazinyl, triazole (4, 5b) pyridazinyl, oxoimidazolyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperacinyl, benzimidazolyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinazolinyl, quinaxalinyl, indolizinyl, quinolizinyl, 1,8-naphthyridinyl, purinyl, pteridinyl, dibenzorphuranyl, carbarolinyl, carbarolyl.

A cyclic group includes, for example, C₃_₆ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl 3247 B; C₃.₆ cycloalkenyl such as 1-cyclopropenyl, 2-cyclobutenyl, 1-cyclohexenyl, 2-cyclohexenyl and 1,3-cyclohexenyl and 1,3-cyclohexadien-1-yl; C₆.₁₀ aryl such as phenyl and naphthyl.

(I) C_x.₄ alkylated groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, fluorobutyl, tert-butyl and the like.

(II) C₃_₆ cycloalkyl groups include, for example, cyclopropyl, cyclopropinyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

(III) C₆_₁₀ aryl groups include, for example, phenyl, naphthyl and the like.

(IV) C_x_₄ alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tertiary butoxy and the like.

(V) C₃_₆ cycloalkoxy groups include, for example, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy and the like.

(VI) C₆.₁₀ aryloxy groups include, for example, phenoxy, naphthyloxy and the like.

(VII) C₇_₁₂ aralkyloxy groups include, for example, benzyloxy, 2-phenethyloxy, 1-phenethyloxy and the like.

(VIII) C₁.₄ alkylthio groups include, for example, methylthio, ethylthio, propylthio, butylthio and the like.

(IX) C₃_₆ cycloalkylthio groups include, for example, cyclopropylthio, cyclopropentylthio, cyclohexylthio and the like.

(X) (XI) (XII) (XIII) (XIV) (XV) (XVI) (XVII)

C₆.₁₀ arylthio groups include, for example, phenylthio, naphthylthio and the like.

C₇_₁₂ aralkylthio groups include, for example, benzylthio, 2-phenethylthio, 1-phenethylthio and the like.

Mono-C_x_₄ alkylamino groups include, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert-butylamine and the like.

Di-C₁_₄ alkylamino groups include, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-N-ethylamine, N-methyl-N-propylamine, N-methyl-N-butylamine and the like.

C₃_₆ cycloalkylamino groups include, for example, cyclopropylamine, cyclopentylamine, cyclohexylamine and the like.

C₆_₁₀ arylamino groups include, for example, aniline and the like.

C₇.₁₂ aralkylamino groups include, for example, benzylamine, 2-phenethylamine, 1-phenethylamine and the like.

Halogens include, for example, fluorine, chlorine, bromine, iodine and the like.

C_x.₄ alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, isobutoxycarbonyl and the like.

(XVIII) (XIX) C₆.₁₀ aryloxycarbonyl groups include, for example, phenoxycarbonyl and the like.

(XX) C₃_₆ cycloalkoxycarbonyl groups include, for example, cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexoxycarbonyl and the like.

(XXI) C₇_₁₂ aralkyloxycarbonyl groups include, for example, benzyloxycarbonyl, 1-phenethyloxycarbonyl, 2-phenethyloxycarbonyl and the like.

(XXII) C_x_₅ alkanoyl groups include, for example, formyl, acetyl, propionyl, butyryl, pivaloyl and the like.

(XXIII) C_x.₁₅ alkanoyloxy groups include, for example, formyloxy, acetyloxy, butyryloxy, pivaloyloxy, pentaloyloxy, hexanoyloxy, geptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy and the like.

(XXIV) Optionally substituted carbamoyl groups include, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, pyrrolidinecarbamoyl, piperazinecarbamoyl, piperazinecarbamoyl, piperazinecarbamoyl.

(XXV) Optionally substituted carbamoyloxy groups include, for example, N-methylcarbamoyloxy, N, N-dimethylcarbamoyloxy, N-ethylcarbamoyloxy, N-benzylcarbamoyloxy, N, N-dibenzylcarbamoyloxy, N-phenylcarbamoyloxy and the like.

(XXVI) (XXVII) (XXVIII) (XXIX) (XXX) (XXXI) alkanoylamino groups include, for example, formylamine, acetamide, propionamide, butyrylamide and the like.

C₆_₁₀ arylcarbonylamino groups include, for example, benzamide and the like.

alkoxycarbonylamino groups include, for example, methoxycarbonylamine, ethoxycarbonylamine, butoxycarbonylamine, tert-butoxycarbonylamine and the like.

C₇_₁₂ aralkyloxycarbonylamino groups include, for example, benzyloxycarbonylamine, 4-methoxybenzyloxycarbonylamine, 4-nitrobenzyloxycarbonylamine, 4-chlorobenzyloxycarbonylamine and the like.

Substituted sulfonylamino groups include, for example, methanesulfonylamine, ethanesulfonylamine, butanesulfonylamine, benzenesulfonylamine, toluenesulfonylamine, naphthalenesulfonylamine, trifluoromethanesulfonylamine, 2-chloroethanesulfonylamine, 2,2,2-trifluoroethanesulfonylamine and the like.

Heterocyclic groups are cyclic groups and each has from 1 to 5 heteroatoms selected from nitrogen, oxygen and sulfur and includes, for example, pyrrolidinyl, 2- or 3-pyrrolyl,

3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 2- or 3-furyl, 2- or 3-thienyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 2-,

4- or 5-thiazolyl, piperidinyl, 2-, 3- or 4-pyridyl, piperazinyl, pyrimidinyl, pyranyl, tetrahydropyranyl, tetrahydrofuryl, indole, quinolyl, 1,3,4-oxadiazolyl, thieno (2,3- d) pyridyl, 1,2,3-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, tetrazole (1,5- b) pyridazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl and the like.

(XXXII) Heterocyclylthio, heterocyclyloxy, heterocyclylamino and heterocyclylcarbonylamino groups are heterocyclic groups attached through a sulfur, nitrogen and carbonyl atom, respectively, wherein the heterocyclic moiety is the aforementioned group (XXXI).

(XXXIII) Di-C_x_₄ alkylphosphinothioylamine groups include, for example, dimethylphosphinothioylamine, diethylphosphinothioylamine and the like.

(XXXIV) Alkoximine groups include, for example, methoximine, ethoximine, 2-phthorethoximine, carboxymethoximine, 1-carboxy-1-methylethoxyimine,

2,2,2-trichloroethyloxycarbonylmethoxyimine, 1- (2,2,2-trichloroethyloxycarbonyl) -1-methylethoxyimine, (2-amino-thiazol-4-yl) methoxy-imine, (1H-imidazol-4-yl) -methoxy-amine and the like.

(XXXV) C_x_₄ alkylsulfonyloxy groups include, for example, methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy and the like.

(XXXVI) C₆__X0 arylsulfonyloxy groups include, for example, benzenesulfonyloxy, toluenesulfonyloxy and the like.

(XXXVII) Di-C₆__X0 arylphosphinothioylamine groups include, for example, diphenylphosphinothioylamine and the like.

(XXXVIII) Optionally substituted thiocarbamoylthio groups include, for example, thiocarbamoylthio, N-methylthiocarbamoylthio, N, N-dimethylthiocarbamoylthio, N -ethiothiocarbamoylthio, N-benzothiocarbamoylthio, N, N-dibenzylthiocarbamoylthio, N-phenylthiocarbamoylthio.

(XXXIX) Silyloxy groups include tri-C₁_₄ alkylsilyloxy groups such as trimethylsilyloxy and tert-butyldimethylsilyloxy mixed Ο_χ.₄ alkylphenylsilyloxy groups such as tert-butyldiphenylsilyloxy, dimethylphenylsilyloxy and the like.

(XL) Silyl groups include tri-C₁.₄ alkylsilyl groups such as trimethylsilyl and tert-butyldimethylsilyl, mixed C_x_₄ alkylphenylsilyl groups such as tert-butyldiphenylsilyl, dimethylphenylsilyl and the like.

(XLI) C_x_₄ alkylsulfinyl groups include, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl and the like.

(XLII) C₆_₁₀ arylsulfinyl groups include, for example, phenylsulfinyl, naphthylsulfinyl and the like.

(XLIII) C_x_₄ alkylsulfonyl groups include, for example, methanesulfonyl, ethanesulfonyl, butanesulfonyl and the like.

(XLIV) Arylsulfonyl groups include, for example, benzenesulfonyl, toluenesulfonyl and the like.

(XLV) C_x.₄ alkoxycarbonyloxy groups include, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy and the like.

(XLVI) C_x_₄ haloalkyl groups include C_x_₄ alkylating groups with 1-4 halogen atoms such as trifluoromethyl, 1, 1,2,2-tetrafluoromethyl, difluoromethyl, monofluoromethyl, trichloromethyl, dichloromethyl, monochloromethyl and the like.

(XLVII) C _x_₄ haloalkyloxy, C_x_₄ haloalkylthio, C_x_₄ haloalkylsulfinyl and sulfonyl group include haloalkyl h-;₄ haloalkyl, for example, attached

C 1-4 through groups, oxygen, sulfur and nitrogen, sulfinyl and sulfonyl, respectively, where C_t_₄the haloalkyl moiety is the aforementioned group (XLVI).

(XLVIII) Cyano, nitro, hydroxyl, carboxyl, sulfo (SO₃H), and phosphone (-PO₃H₂) .

(XLIX) C_x_₄ alkyloxysulfonyl groups include, for example, methoxysulfonyl, ethoxysulfonyl, butoxysulfonyl and the like.

(L) ^CAryloxysulfonyl groups of 6 include, for example, phenoxysulfonyl, tolyloxysulfonyl and the like.

(LI) C₇_₁₂ aralkyloxysulfonyl groups include, for example, benzyloxysulfonyl, 2-phenethyloxysulfonyl, 1-phenethyloxysulfonyl and the like.

(LII) Di-C₁_₄ alkyloxyphosphoryl groups include, for example, dimethoxyphosphoryl, diethoxyphosphoryl, dibutoxyphosphoryl and the like.

Among the compounds of formula (I) above, more preferred examples of the invention are compounds of formula:

.la (I^c') in which R^la is mono-C1-6 alkylamine, N-Cx_6 alkyl-Nformylamine or an amine, R^2a is Cx_₄ alkyl or C_x_₄alkoxyl and A^a is chloropyridyl;

, 1b

ON (Λ '

NH: h₂—-A * wherein R^lb is mono-C₁.₆ alkylamine or Ν-0_χ_₆ alkyl-Nformiamine, and A^a have the same meanings as defined above;

Ic

2b: h₂—&lt;

(i^c) in which R^lc is di-C1.6 alkylamine, R^2b is hydrogen, formyl or Cx_₄ alkyl and A^b is pyridyl or chloropyridyl; or .1 {Iⁿ), '; C:

wherein each group has the same meaning as above; or their agrochemically acceptable salts.

Mono-C₁_₆ alkylamino group R^la and R^lb in formulas (Ia), (Ib) and (Ic) include, for example, monomethylamine, monoethylamine, mono-n-propylamine, mono-iso-propylamine, mono-n-butylamine, mono-n-hexylamine and the like. Better such mono-C._wow examples of alkylamine include mono-C₁.₄ alkylamine such as monomethylamine and monoethylamine.

NC

1-6 alkyl-N-formylamino groups, 1b

R and R include,

For example, N-ethyl-N-formylamine, N-methyl-N-formylamine, N, N-propyl-N-formylamine, N-isopropyl-N-formylamine, Nn-butyl-N-formylamine, Nn-hexyl-N- formylamine and the like. Preferred examples of such NC4g-alkyl-Nformylamino groups are NC_x_₄ alkyl-Nf ormylamines such as formylamine.

N-methyl-N-formylamine and N-ethyl-NDi-C_x_₆ alkylamino R groups include, for example, dimethylamine, N-ethyl-N-methylamine, diethylamine, di-n20 propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-n-pentylamine, di-iso- pentylamine, di-n-hexylamine and the like. Better such di-C_x_₆examples of alkylamino groups include di-C₁.₄ alkylamines such as dimethylamine, N-ethyl-N- methylamine and diethylamine.

C_x_₄ alkylated by R^2a and R^2c includes, for example, the groups specified for Rs². Better such C_x.₄examples of alkyl groups include methyl, ethyl and the like.

C_x_₄ alkoxy groups on R^2a includes, for example, the groups mentioned above for Rs². Better such C_x_₄ examples of alkoxy groups include methoxy, ethoxy and the like.

A^a and A^b chloropyridyl groups include, for example, 2chloro-3-pyridyl, 4-chloro-3-pyridyl, 5-chloro-3-pyridyl, 6-chloro-3-pyridyl, 3-chloro-4-pyridyl and the like. Preferred examples of such chloropyridyl groups include 6-chloro-3-pyridyl and the like.

A^b pyridyl groups include, for example, 3-pyridyl, 4pyridyl and the like. Preferred examples of such groups are 3-pyridyl and the like.

Among the compounds represented by formula (I) above

<td>better than this formulas:</td><td>of the invention</td><td>examples</td><td>are compounds</td>

<td></td><td>z * , oh HR</td><td>7 a n^2c</td><td></td>

<td></td><td> 1</td><td>Ϊ</td><td rowspan="2">A^C 'J' ·</td>

<td>r&gt; - Λ .r ~~ x^2a/</td><td>- c</td><td>- N · CH n 2 n</td>

in which X^2a is hydrogen, Cx-4 alkoxycarbonyl or Cx-4 alkylsulfonylthiocarbamoyl; R^2c is hydrogen, Cx_₃acyl, C_x.₄ alkyl, mono or di-C_x_₄ alkoxy-C_x_₄alkyl, C₇.₈ aralkyl, mono- or di-C_x_₄ alkylamine or C_x_₄ alkoxy; A^c is 3- or 4-pyridyl, pyrazinyl or 4- or 5-thiazolyl optionally substituted with halogen, Cx-4 alkyl or Cx-4 alkoxy; R^6a and R^7a is hydrogen, lower alkyl, halogenated lower alkyl, or Cx-₄ acyl; n has the same meanings as above;

c&gt;₂n _Rsee

NC H- n 2n {I^f) 'in which X^2a is hydrogen, C_x_₄ alkoxycarbonyl or

C_x_₄ alkylsulfonylthiocarbamoyl; R^see is an amine, monoLT 3247 B or di-C ^^ alkylamine, NC_x_₄ alkyl-NC ^ acylamine, C₇.₉ aralkylamine, halo-thiazolyl-C₁.₂ alkylamine or

<td colspan="2">C_x_₄ alkoxy-C₁.₂ alkylamine;</td><td colspan="2">2c R is hydrogen, C_x_₃</td>

<td>acyl, C_x_₄ alkyl,</td><td>mono-</td><td>or di-C_x_₄</td><td>alkoxy-C_x_₄</td>

<td>alkyl, C₇_₈ aralkyl,</td><td>mono-</td><td>- or di-C₁.₄</td><td>alkylamine</td>

<td>or C_x.₄ alkoxy; n is</td><td> 0, 1</td><td>or 2; A^d is</td><td>3- or 4-</td>

<td>pyridyl, pyrazinyl</td><td>or</td><td>5-thiazolyl,</td><td>not necessarily</td>

substituted by halogen, C_x_₄ alkyl or C_x_₄ alkoxy;

2^N ? bJ e, 2d

<img file="LT3247B_D0007.tif" />

(V)

<td>in which X^2b</td><td>is hydrogen or</td><td colspan="2">C_x_₂ alkylsulfonyl</td>

<td colspan="2">thiocarbamoyl; R^la is an amine,</td><td>mono- or</td><td>di ^&lt;3_x_₂</td>

<td>alkylamine</td><td colspan="2">or NC_x.₂ alkyl-N-formylamine;</td><td>“2d R is</td>

<td>hydrogen</td><td>or C_X-₃ acyl; and A^e</td><td>is a group</td><td>having</td>

<td>formula:</td><td></td><td></td><td></td>

<img file="LT3247B_D0008.tif" />

wherein Hal is halogen;

°₂·;

, lf

2d

CH.

(i^h), 2c where X^2c is hydrogen or methylsulfonylthiocarbamoyl; R^lf is an amine, methylamine, dimethylamine or N-methyl-N-formylamine; R^2d is hydrogen, formyl or C_x_₂ alkyl; and A^e is a group of the formula:

<img file="LT3247B_D0009.tif" />

wherein Hal is halogen; or

- CH - Hal (I¹) in which R^down is an amine, mono- or di-C 1-2 alkylamine or N-C 1-2 alkyl-N-formylamine; R^2e is Cx_₂ alkyl or formyl; and Hal is halogen; or their agrochemically acceptable salts.

In the formulas (Ι^θ) - (I¹) groups marked with an X^2a, X^2b and X^2c;

R^see, R^down and R^lf; R^2c, R^2d and R^2e; and A^c, A^b and A^e, is. 2 12,,,, groups mentioned in X, P, P, A, respectively. In groups marked with R^6a and groups labeled R^7a, there are groups labeled R⁶ and R⁷, respectively.

The compounds represented by the formula (I) and their salts can be obtained in EP-A-0104/001. No. 30,2389 (Japanese Patent Application No. 171/1990, the disclosure of which is incorporated herein by reference), or analogous to methods known in the art.

In the above formula (II), R, R and R are hydrogen; Ο_χ_₃ acyl groups including alkanoyl groups such as formyl, acetyl and propionyl; alkylating groups such as C_x_₄ alkylating groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and fluoro-butyl; alkenyl groups such as C₂_₄ alkenyl groups such as vinyl and gold; alkynyl groups such as C₂_₄ alkynyl groups such as ethynyl, 1-propynyl, and 2-propynyl; cycloalkynyl groups such as C₃_₆ cycloalkynyl groups such as cyclopentyl and cyclohexyl; or heterocyclic groups linked through a carbon atom (including said B groups) such as pyridinyl groups such as

3- or 4-pyridyl.

The Rs of this group⁸, R⁹ and R¹⁰ may have 1-3 (preferably 1) substituted groups which are the same or different. Examples of such substituted groups include, but are not limited to, C_x_₄ alkylthio groups such as methylthio and ethylthio; C_x,₄ alkoxy groups such as methoxy and ethoxy; mono- or di-C₁_₄ alkylamino groups such as methylamine, ethylamine and dimethylamine; C₂.₅alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; C_x_₄ alkylsulfonyl groups such as methylsulfonyl and ethylsulfonyl; halogens such as fluorine, chlorine, bromine and iodine; C_x_₄ acyl groups including alkanoyl groups such as acetyl, benzoyl; phenylsulfonyl and pyridyl.

With better Rs⁸, R⁹ and R¹⁰ examples include hydrogen; C_x_₃acyl groups including alkanoyl groups such as formyl, acetyl and propionyl, and alkylating groups such as C_x_₄ alkylating groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and fluorobutyl.

With even better Rs⁸, R⁹ and R¹⁰ examples include hydrogen;

C_x_₃ alkanoyl groups such as formyl, acetyl and propionyl; and C_x_₄ alkylated groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and fluorobutyl.

In the above formula (II) B is a substituted or unsubstituted heterocyclic group having a simple or fused ring with 5 or 6 ring members in each ring. In particular examples, suitable 5- or 6-membered heterocyclic groups include pyridyl groups such as 2-, 3- or 4-pyridyl, thiazolyl groups such as 2-, 4- or 5-thiazolyl, and pyrazinyl groups.

These heterocyclic groups may have 1-5 (preferably 1) substituted groups which are the same or different. Examples of such groups include, but are not limited to, (1-4C) alkylating groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, fluorobutyl and tert-butyl; (1-4C) alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and tert-butoxy; (1-4C) alkylthio groups such as methylthio, ethylthio, propylthio and butylthio; halogen atoms such as fluorine, chlorine, bromine and iodine; (1-4C) haloalkyl groups such as trifluoromethyl, 1,1,2,2-tetrafluoromethyl, difluoromethyl, monofluoromethyl, trichloromethyl, dichloromethyl and monochloromethyl; (1-4C) haloalkoxy groups; (1-4C) haloalkylthio groups; (1-4C) haloalkylsulfinyl groups; or (1-4C) haloalkylsulfonyl groups wherein said C (1-4) haloalkyl group is attached via an oxygen or sulfur atom, or a sulfinyl or sulfonyl group; cyano; nitro; hydroxyl; carboxyl; sulfo (-SO₃O); and phosphon {PO₃H₂) .

More preferred examples of B are five- or six-membered heterocyclic groups such as pyridyl and thiazolyl which may be substituted by one or two halogens. Specific examples of B are 3-pyridyl,

4-pyridyl, halo-pyridyl such as 6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl and

5-bromo-3-pyridyl, 6-methoxy-3-pyridyl, 6-methyl-3-pyridyl, 2-thiazolyl, 4-thiazolyl, halo-thiazolyl such as 2-chloro-5-thiazolyl and 2-bromo-5-thiazolyl, 2- pyrazinyl.

Even more preferred examples of B are 3-pyridyl, 4-pyridyl, 6-chloro-3-pyridyl, 6-bromo-3-pyridyl,

6-fluoro-3-pyridyl, 5-bromo-3-pyridyl, 6-methoxy-3-pyridyl, 6-methyl-3-pyridyl, 2-thiazolyl, 4-thiazolyl, 2-chloro-5-thiazolyl, 2-bromo- 5-thiazolyl, 2-pyrazinyl.

A preferred embodiment of the compounds represented by formula (II) above is a compound of the formula:

10a

R

<img file="LT3247B_D0010.tif" />

R

C = CH - NO a

(Ha) in which B^a is a substituted or unsubstituted pyridyl or thiazolyl group, and R^8a, R^9a and R^10a each independently is hydrogen; alkyl, alkenyl, alkynyl, cycloalkyl, acyl or alkoxycarbonyl; or an agrochemically acceptable salt thereof.

In the above formula (Ha) it is preferable that B^a is a halogenated group such as a group of the formula:

<img file="LT3247B_D0011.tif" />

where Hal is halogen.

Among the compounds of formula (Ha) above, preferred compounds are those of the formula:

10b

<img file="LT3247B_D0012.tif" />

R^9b - N

CH

N '

8b

C = CH-NO (Hb) in which R^8b, R^9b and R^10b each independently is hydrogen or alkyl and Hal is halogen, or

R^10c

<img file="LT3247B_D0013.tif" />

in which R^8c, R^9c and R^10c each is independently hydrogen or alkyl, and Hal is halogen or an agrochemically acceptable salt thereof.

The compounds of formula (II) and their salts may be obtained by methods known in the art. The compounds of the formula (II) and their salts may also be prepared by the methods described in the present application EP-A-1/00. 302389 (corresponding to Japanese Patent Application No. 171/1990).

In the case where the compound (I) or (II) is obtained in the free form, it can be converted into the corresponding salt by conventional means. When compound (I) or (II) is obtained in its salt form, it can be converted into the free compound by conventional methods.

In the case where the compound (I) or (II) has at least one acidic group such as a carboxyl, sulfo (-SO₃H) and phosphone (-PO₃H₂), (I) or (II) may form an alkali salt. Examples of such alkali include inorganic alkali such as sodium, potassium, lithium, calcium, magnesium and ammonium alkali and organic alkali such as pyridine, collidine, triethylamine and triethanolamine.

In the case where the compound (I) and (II) contains at least one alkali group such as an amino or a substituted amino group, the compound (I) or (II) may be replaced by an acid addition salt. Examples of such acid-addition salts include salts with inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid and phosphoric acid, as well as organic acids such as acetic acid, benzoic acid, fumaric acid. acid, succinic acid, tartaric acid, citric acid, oxalic acid, glyoxalic acid, aspartic acid, methanesulfonic acid, methanesulfonic acid, 1,2-ethanedisulfonic acid and benzenesulfonic acid.

Examples of representative α-unsaturated amine derivatives represented by formulas (I) and (II) that may be used in the composition of the present invention include:

(Compound No. 1) 1- [N- (6-Chloro-3-pyridylmethyl) -N-methyl] amino-1-methylamino-2-nitroethylene;

(compound # 2)

1- (6- (chloro-3-pyridylmethyl) amino-1-dimethylamino-2-nitroethylene;

(compound # 3)

1- [N- (4-chloro-3-pyridylmethyl) -N-ethyl] amino-1-methylamino-2-nitroethylene;

(compound # 4)

1- [N- (6-chloro-3-pyridylmethyl) -N-methyl] -amino-1-dimethylamino-2-nitroethylene;

(compound # 5)

1- [N- (6-chloro-3-pyridylmethyl) -N-ethyl] amino-1- (Nformyl-N-methyl) amino-2-nitroethylene;

(Compound No. 6) - [N- (2-Chloro-5-thiazolylmethyl) -N-ethyl] -amino-1-methylamino-2-nitroethylene;

(compound # 7)

1- [N- (2-Chloro-5-thiazolylmethyl)] amino-1-methylamino-2-nitroethylene;

(Compound No. 8) 1- [N- (6-Bromo-3-pyridylmethyl) -N-methyl] -amino-1-methylamino-2-nitroethylene;

(Compound No. 9) 1- [N- (6-chloro-3-pyridylmethyl) -N-formyl] amino-1-dimethylamino-2-nitroethylene;

(Compound No. 10) 1- [N - '(6-Fluoro-3-pyridylmethyl) -N-methyl] -amino-1-methylamino-2-nitroethylene;

(compound #ll)

1- (N-Ethyl-N- (6-fluoro-3-pyridylmethyl) -amino-1-methylamino-2-nitroethylene;

(compound no.12)

1- [N- (6-bromo-3-pyridylmethyl) -N-ethyl] -amino-1-methylamino-2-nitroethylene;

(compound # 13) 1- [N- (2-Chloro-5-thiazolylmethyl) -N-methyl] -amino-1- (N-formyl-N-methyl) amino-2-nitroethylene;

(Compound # 14) 1- [N- (2-Chloro-5-thiazolylmethyl) -N-ethyl] amino-1- (N-formyl-N-methyl) amino-2-nitroethylene;

(compound # 15)

1- [N- (6-bromo-3-pyridylmethyl) -N-methyl] amino-1- (Nformyl-N-methyl) amino-2-nitroethylene;

(Compound No.16) 1- [N- (6-Bromo-3-pyridylmethyl) -N-ethyl] amino-1- (Nformyl-N-methyl) amino-2-nitroethylene;

(Compound No. 17) 1- [N- (6-Bromo-3-pyridylmethyl) -N-formyl] amino-1-dimethylamino-2-nitroethylene;

(compound no.18)

1- [N- (6-chloro-3-pyridylmethyl) -N-2,2,2-trifluoroethyl] amino-1-methylamino-2-nitroethylene;

(compound no.19)

1- [N- (2-chloro-5-thiazolylmethyl) -N-formyl] amino-1-dimethylamino-2-nitroethylene;

(compound no.20)

1- (6-chloro-3-pyridylmethyl) amino-1-methylamino-2-nitroethylene;

(Compound # 21) 1-Amino-1- [N- (6-chloro-3-pyridylmethyl) -N-methyl] amino-1-methylamino-2-nitroethylene;

and analogous.

α-Unsaturated amino derivatives or their salts can be used as insecticides according to the technology described in the patent no. 302389 (conforming to Japanese requirements, EP 171/1990, under EP Patent Application).

The present inventors have noted that α-unsaturated amino derivatives or their salts can be stabilized to a significant extent by long-term storage and exposure to light in the form of agrochemicals using acids and specific solid carriers.

The inventors have also found that α-unsaturated amine derivatives or their salts can be incorporated into adsorbable solid carriers together with various agrochemical fillers, thereby significantly increasing the described stability of the α-unsaturated amine derivatives or their salts for long-term storage, and photostability.

In one aspect of the invention, the inventors have been fortunate in obtaining aqueous solutions of the agrochemically active component (the anesthetic amine derivative or its salt) having a pH of 5.5 or lower (or suspensions) and combining the above solution (or suspension) with the above stabilizer (solid). carrier capable of adsorbing), to obtain a composition or formulation which results in an unexpectedly prolonged lifetime of the α-unsaturated amino derivatives or their salts and improved light resistance.

The acids used in the invention include inorganic and organic acids. Examples of inorganic acids include perchloric acid, hydrochloric, sulfuric, nitric, phosphoric, and the like. Examples of organic acids include L-ascorbic, acetic, succinic, benzoic, aspartic, citric, glutamic, oxalic, trichloroacetic, lactic, dichloroacetic, fumaric, maleic, malic, malonic, benzoic, acid isopropyl phosphate and others. The best examples are strong acids (those with an O dissociation constant greater than approximately 1x10 ³ or their pH is less than 3 (Iwanami Rikagaku Jiten, 3rd ed., 1971, Iwanami Publishing Company, Japan). In such cases, any of the inorganic and organic acids may be used, but inorganic acids are preferred. Better examples are given below. Such inorganic acids include perchloric acid, hydrochloric, sulfuric, nitric, phosphoric and the like. Such organic acids include aspartic acid, citric acid, glutamic acid, oxalic acid, dichloroacetic acid, trichloroacetic acid, fumaric acid, maleic acid, malonic acid, benzenesulfonic acid, acidic isopropyl phosphate and the like.

Preferred are phosphoric acid, hydrochloric acid, oxalic acid, citric acid, benzenesulfonic acid, acidic isopropyl phosphate and others. Even better are phosphoric acid, citric acid, benzenesulfonic acid, acidic isopropyl phosphate, and others. Phosphoric acid is most suitable. Other carriers capable of incorporating α-unsaturated amino derivatives or salts thereof of (I), (II) are used in the invention. Such solid carriers include carriers capable of adsorbing at least 5.0x10 mmol / g of active substance and a solution or suspension having a pH of less than or equal to 5. In general, solid carriers capable of adsorbing 5.0x10-400x10 mmol / g of active substance are used. Carriers that are capable of adsorbing 10.0 x 10 to 200 x 10 mmol / g active substance, more preferably 10.0 x 10 to 100 x 10 mmol / g active substance, are preferred.

Examples of such solid carriers include mineral clays capable of adsorbing zeolites, activated carbon, betacyclodextrin, and the like. Examples of such molar minerals include montmorillonitaponite groups having a structural crystal type of 2: 1 and sepiolite having a structural crystal type of double-chain forms. The best examples of these are montmorillonitaponite groups with a structural crystal type of 2: 1.

Examples of such montmorillonite-saponite clay minerals include montmorillonite, beidelite, nontronite, saponite, hectorite, sauconite, as well as minerals containing as the main constituent any of montmorillonite, beidelite, montronite, saponite, hectorite, fuller earth, bentonite, white earth, and activated fuller earth. It is better to have a fuller earth.

Other carriers capable of adsorbing are not limited to the carrier examples described above, but may include any material capable of inserting α-unsaturated amino derivatives (I), (II) or their salts, or capable of inserting (or surrounding themselves) other material or metasomatic a mineral obtained by substitution to form a complex such as an insert complex and a clathrate.

As the adsorption properties of common mols and kaolin are not sufficient, they do not increase the stability. It follows that they are not suitable for the present invention as solid carriers capable of adsorbing.

The solid carrier of the present invention is generally used in powder form. The particle size is in the range of 100 μπι or less, the usual size being 1-100 μπι, more preferably 10-80 μπι. A size of 20-50 μπι is best.

The amount of solid carrier (total amount when two or more carriers are used) in the composition of the invention is 1-95% by weight, respectively, of the total weight of the final formulation.

For example, for dusts, DL dusts, granules and aikroaranules F, a range of about 1-90% by weight, preferably about 1-30% by weight, is suitable. Moisturizing powders and moisturizing granules, etc. in the case of this range is about 5% by weight, preferably about 50-90% by weight. The amount of film carrier (total when two or more carriers are used) is about 10 parts by weight or more per part by weight of the active component, preferably about 10 to 50 parts by weight, more preferably 10 to 20 parts by weight.

The acid content (total amount when two or more acids are used) in the composition of the invention is preferably about 0.0001-10% by weight of pure acid for the total weight of the final formulation. For example, in the case of dust, DL dust, pellets and F microgranules, a range of about 0.0005-5% by weight, preferably about 0.0005-3% by weight, is suitable. And wetting powders and wetting pellets and so on. in the case of about 0.5-10% by weight, preferably about 0.5-5% by weight.

The amount of acid specified (total amount when using two or more acids) is from about 0.05 to about 0.5 parts by weight per solid carrier weight, preferably from about 0.1 to about 0.3 parts by weight.

The amount of the α-unsaturated amine derivative or salt thereof in the composition of the invention is about 0.1 to 90% by weight of the total weight of the final formulation. For example, in the case of dusts, DL dusts, granules and F microgranules, the respective amounts are about 0.1-10% by weight, while wetting powders, wetting pellets and the like. in the case of about 5-90% by weight.

The amount of solid carrier (total when two or more solid carriers are used) is from about 0.1 to about 100 parts by weight per part by weight of the α-unsaturated amine derivative or salt thereof, preferably from about 0.5 to about 50 parts by weight.

The agrochemical composition of the present invention may be prepared or prepared by conventional techniques to adjust the pH of the resulting concentrated agrochemical dust. In one embodiment, the agrochemical compositions are prepared or prepared by incorporating or coating the active ingredient in another vehicle at pH 5.5 or less. For example, such preparations include:

(1) obtaining an aqueous solution (or suspension) of at least one of the active substances, adjusting their pH to 5.5 or less, and then mixing (or remixing) the resulting formulation with a solid carrier, if necessary in admixture with another agrochemical adjuvant, the active ingredient in another carrier;

(2) obtaining an aqueous solution (or suspension) of at least one of the active substances and mixing the acid with a solid carrier, if necessary in admixture with other agrochemical adjuvants, wherein the amount of acid in the resulting composition (or suspension) is sufficient to adjust the pH to 5.5; less, and subsequently mixing the resulting aqueous solution (or suspension) with the resulting mixture by adding the active ingredient to a solid carrier;

(3) mixing at least one of the active substances, the solid carrier and the acid with at least one other solid carrier, wherein the amount of acid in the resulting composition is used, to adjust the pH to 5.5 or less and then mixing the resulting mixture with water (or aqueous solution or suspension) by incorporating the active ingredient in a solid carrier; or (4) mixing at least one of the active substances and a carrier with a solid solid at least a carrier, and then mixing the resulting mixture with an aqueous solution (or suspension) containing the acid, adding the active ingredient in a solid carrier sufficient to form the resulting composition. Adjust the pH to 5.5 or less when the aqueous solution (or suspension) is mixed with the mixture.

one of the others

Mixing or mixing can be done with a mixer such as a mortar and pestle or dough mixer. The mixing is not limited to the techniques described, but may include any of the agrochemicals or formulation technologies well known to those skilled in the art. For example, one embodiment may be that after mixing and insertion, moisture may be removed by drying.

Thus, according to the invention, and using the methods set forth herein, it is important to adjust the pH of the solution (or suspension) containing the active ingredient, etc., to 5.5 and less before incorporation of the given active ingredient into or with a stabilizer. Its pH is usually adjusted to 0.01-5.5, preferably 0.014.0, and more preferably 0.1-3.0. More preferably, the solution (or suspension) used in the practice of the invention has a pH of about 3.0.

(1) and (4) a few drops of solution {ar

For example, the pH in the above processes can be adjusted by adding phosphoric acid to 500 ml of aqueous suspension). However, pH can be adjusted with buffer solutions and the like without limitation. In the above processes (2) and (3), the pH can be easily adjusted by adding a few drops of phosphoric acid to the solid carrier.

Aqueous solvent (or suspension) solvents for use in the present invention include water as well as water miscible organic solvents. The preferred systems of the present invention are those which, depending on the agrochemical agents or formulations, contain only water. The stabilized compositions of the invention are substantially tolerant to plants and animals (including fish) when used and after use.

The composition of the present invention is thus safe (harmless) and stable.

The composition of the invention is in solid form. The composition may be used as a suitable agrochemical solid or as a dusting preparation, DL (non-washable) dust, granules, wettable powder, water-dispersible granules, grain dressing agents and microgranules F.

Such compositions may be admixed or formulated with other agrochemically active components and / or agrochemically acceptable carriers such as dispersants, dispersants, wetting agents, adhesives, anti-blocking agents, agglomerating agents, binders, antioxidants, drying agents and the like.

etc.

Conventional solid carriers (diluents / fillers) preferably include mineral powders such as clays (e.g., finely ground clay), etc., talc (e.g., talcum powder, agalmatolite powder, etc.), silica (e.g., diatomaceous earth, mica powder, and etc.), vegetable flour (for example, soy flour, tobacco flour, wheat flour, sawdust, etc.), calcium carbonate, sulfur powder, urea powder and the like. Any auxiliary agent may be used for this purpose, provided that it is agrochemically appropriate. Those solid carriers may be used individually or in a suitable blend of two or more components in suitable proportions.

Surfactants include, as appropriate, dispersants, dispersants, wetting agents or penetrants, and various soaps and nonionic or anionic surfactants such as polyoxyethylene alkylaryl ethers (e.g., Noigen ™ and EA 142 ™, Daiichi Kogyo Seiyaku KK), sodium alkylnaphthalenesulfonates (e.g. Newcalgen BX-C ™, Takemoto Yushi K. K.), block copolymers of ethylene oxide and propylene oxide (e.g. Newpolas PE-64 ™, Sanyo Kasei KK), polycarboxylate-type surfactants (e.g. Toxanone GR-30 ™, Sanyo Kasei KK), dialkylsulfoglycerate, sodium ester (e.g. , Neocolas SW-C ™, Dai-ichi Kogyo Seeiyaku KK), Polyoxyethylenedistyrenephenyl ether sulfate ammonium salts (e.g. Dicosol 60A ™, Dai-ichi Kogyo Seiyaku KK), sodium lignin sulfonates and potassium lignin sulfonates.

Surfactants which may be used as dispersants, dispersants, wetting agents or penetrants include different nonionic and anionic surfactants. Best examples of surfactants are:

(1) non-ionic surfactants, as follows:

- polyoxyethylene alkylaryl ethers - (e.g. Noigen ™ and Ε Ε 142 ™, Dai-ichi Kogyo Seiyaku KK),

- ethylene oxides and block copolymers of propylene oxide (e.g. Njupol PE-64 ™, Sanyo Kasei KK).

(2) anionic surfactants, as follows:

- polycarboxylate surfactants (for example, Toksanon GR-30 ™, Sanyo Kasei KK),

- salts of dialkyl sulphoglyceric acid (eg Neokol · Kogyo Seiyaku KK), sodium ester

SW-C ™, Dai-ichi

- ammonium salts of polyoxyethylene distyrenophenyl ether (e.g. Dikszol Dikszol WK ™, Dai-ichi Kogyo Seiyaku K.

sulfate 60A ™ and

K.),

- New Calgary alkyl naphthalenesulfonates BX-C ™, Takemoto Yushi K.

(for example,

K.),

- sodium lignin sulphonate, potassium lignin sulphonate and the like.

Typically, the amount of surfactant that may be used in the composition will be about 0-30% by weight of the total final formulation, respectively. For example, a range of about 0-20% by weight is preferred.

Excipients that provide flow include PAF materials such as acidic isopropyl phosphate, talc, and the like. Such fluid materials are not necessarily used in the composition of the invention.

Typically, the fluid content will be approximately 0-20% by weight of the total weight of the final formulation. For example, a range of about 0-10% by weight is preferred.

Anti-blocking agents include white soot, diatomaceous earth, magnesium stearate, alumina, titanium dioxide and others. Such anti-blocking agents are not necessarily used in the composition of the invention.

The usual amount of anti-blocking agents, respectively, is about 0-50% by weight of the total weight of the final formulation. For example, a range of about 0-20% by weight is preferred.

Agglomerating agents include liquid paraffin, ethylene glycol, diethylene glycol, thietylene glycol, polyisobutylene (e.g., IP Solvent-2835 ™ Idemitsu Kagaku KK) and others. Such agglomerating agents are not necessarily used in the composition of the invention.

Typically, the amount of agglomerating agent is approximately 0-20% by weight of the total weight of the final formulation. For example, a range of about 0.2 to about 10% by weight is preferred.

Binding agents include carboxymethylcellulose sodium, dextrin, starch, polyvinyl alcohol, lignin sulphonate sodium, lignin sulphonate potassium and others. Such binding agents are not necessarily used in the composition of the present invention.

Typically, the amount of binder used is approximately 0-30% by weight of the total weight of the final formulation. For example, a range of about 0.2 to about 10% by weight is preferred.

Antioxidants include dibutylhydroxytoluene, 4,4-thiobis-6-tert-butyl-3-methylphenol, butylhydroxyanisole, paraoctylphenol, mono-, di- or tri- (α-methylbenzyl) phenol, 2,6-di-tert-butyl-4 -methylphenol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate and the like. Such antioxidants are not necessarily used in the composition of the present invention.

The usual amount of antioxidants, respectively, is about 0-30% by weight of the total weight of the final formulation. For example, a range of about 0-10% by weight is preferred.

Drying agents include gypsum, silica gel powder and others. Such drying agents are not necessarily used in the composition of the present invention.

Typically, the desiccant amounts to about 0-30% by weight of the total weight of the final formulation. For example, approximate is better

0.5-20% by weight range.

UV adsorbents include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2-ethoxy-2-ethyl-oxalic acid bisanilide, succinic acid and dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6- tetramethylpiperidine polymer, condensate and others. Such UV adsorbents are not necessarily used in the composition of the present invention.

Typically, the amount of UV adsorbents is approximately 0-20% by weight of the total weight of the final formulation. For example, a range of about 0.5 to about 10% by weight is preferred.

UV spreading agents include titanium dioxide and others. Such spreading materials are not necessarily used in the composition of the present invention.

Typically, the amount of UV spreading agent is approximately 0-90% by weight of the total weight of the final formulation. For example, a range of about 1.0 to 20% by weight is preferred.

The composition containing the α-unsaturated amino derivative or a salt thereof may be used in combination with one or more agrochemically active substances such as fungicides (e.g. organic sulfur fungicides, organic phosphorus fungicides, organic arsenic fungicides, organic chlorine fungicides, etc.). .), insecticides (such as organophosphorus, organochlorine, carbamate, pyrethroid insecticides, etc.), various antibiotics.

Representative examples of the indicated agrochemically active substances include (in brackets after the chemical name common names or abbreviations; they are often quoted here).

carbamate insecticides:

2-Isopropoxyphenyl-11-methylcarbamate (PHC₇ propoxur), o-cumenyl-11-methylcarbamate (MIPC, isoprocarb), o-ant. butyl-11-methylcarbamate (BPMC, phenobucarb),

3.4-xylyl-11-methylcarbamate (MPMC, xylylcarb.), M-tolyl-11-methylcarbamate (MTMC, metalcarb.),

3.5-xylyl-11-methylcarbamate (ChMC),

2- (ethylthiomethyl) phenyl-11-methylcarbamate (ethiofencarb),

1-naphthyl-11-methylcarbamate (11AC, carbaryl), primicarb, bendiocarb, carbofuryl, furathiocarb, carbosulfan, benfuracarb, methomyl and others. ;

pyrethroid insecticides:

cyfluthrin, permethrin, cypermethrin, cigaltrin, fenpropatrine fenvalerate, (RS) α-cyano-3-phenoxylbenzyl (S) -2- (4-difluoromethoxyphenyl) -3-methylbutylate (flucitrinate), fluvalinate, 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (ethofenprox), cycloprotrine, resmethrin, alethrin, pyrethrin, etc .;

organophosphorus insecticides:

MPP (fenthion), 0,0-dimethyl-O- (4-nitro-m-tolyl) thiophosphate (MEP, phenitrothion), propafos, dimethyl p-cyanophenylthiophosphate (CYAP, cyanophos), protiphos, sulprophos, profanophos, EPN, cyanof enf moiety, acephate, EPS (oxide-rophos), disulfoton, thiomethone, PAP (fentoat ··);

Sl, 2-bis (ethoxycarbonyl) ethyldimethyldithiophosphate (malathion), dimethoate, vamidothion, (RS) - (O1) (4-chloro) pyrazol-4-yl-O-ethyl-S-propylthiophosphate (pyraclophos), DEP ( trichlorfon), BRP (inaled), DDVP (dichlorphos), CVP (chlorfenvinphos), CVMP (tetrachlorvinphos), monocrotophos, fosalone, chlorpyrifos-methyl, chlorpyrifos, pirimiphos-methyl, diazinon, etrimphos, methidaphos, dioxabenzofos and others;

organochlorine insecticides:

6, 7, 8, 9, 10, 10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,4,3-benzothioxathiepin-3-oxide (endosulfan) and others .;

other insecticides:

S, S '- [2- (dimethylamino) trimethylene (bis) thiocarbamate] (cartap), 5-dimethylamino-1,2,3-tritianium oxalate (thiocyclam),

S, S'2- (dimethylamino) trimethylene (bis) benzene thiosulfonate] (bensultap),

2-tert-Butylamino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadezin-4-one (buprofezin), fenphenoxuron, diflubenzuron, chlorofluorouron, etc .;

N-Heterocyclic Ergosterol Inhibiting Fungicides:

triflumizole, triforine, etc .;

carboxamide fungicides:

mepronil, flutolonyl, pencicuron, oxycarboxin, etc .;

dicarboximid fungicides:

iprodione, vinclozolin, procymidone, etc .;

benzimidazole fungicides:

benomyl and others;

polyhaloalkylthio fungicides:

captan and others;

organophosphorus fungicides:

0-ethyl-S, S-diphenyl-dithiophosphate (EDDP, edifenphos),

O, O-diisopropyl-S-benzyl-thiophosphate (IBP, iprobenphos), etc .;

organic chlorinated fungicides:

4, 5, 6, 7-tetrachlorothalide (phthalide), tetrachloroisophthalonitrile (TPN, chlorothalonil), pentachlorophenol (PCP), etc .;

organic sulfur fungicides:

zinc ethylenebis (dithiocarbamate) (cineb), magnesium ethylenebis (dithiocarbamate) (mannet), etc .;

arsenicorganic fungicides:

iron methanarsonate (MAF), iron ammonium methanarsonate (MAFA) and others. ;

other fungicides:

diclomezine,

5-methyl-1,2,4-triazole (3,4-o) benzothiazole (tricyclazole), pyrochylone, isoprothiolane,

3-Allyloxy-1,2-benzoisothiazole-1,1-dioxide (probenazole), amylazine, oxolinic acid, dimethirimol, (Z) -2'-methylacetaphenone-4,6-dimethylpyrimidin-2-ylhydrazone (pheromone), etc .;

antibiotics:

validamycin, kasugamycin, mildiomycin, blasticidine S, polyoxin, oxytetracycline and others.

Preferred examples of such active components are validamycin A, cartilage, bensultap, probenazole,

IBP, tricyclazole, ferrimon, etofeprox, fenciLT 3247 B trinate, phthalide, MEP, MTMC, BPMC and others. Preferred examples of such active components are validamycin A, cartap, bensultap, MEP, ferrimon, phthalide and others.

Specific examples of the mixed compositions of the invention include α-unsaturated amino derivatives or salts thereof (I) and (II), validamycin A, (I), (II) α-unsaturated amino derivatives or salts thereof, Cartap, (I), (II) α-unsaturated amine derivatives or their salts, bensultap, (I), (II) anesthetic amino derivatives or their salts, pheromone, phthalide, etc.

The amount of agrochemically active substances, except for the (I), (II) α-unsaturated amino derivatives or their salts, in the mixed composition is the same as above. That is, it corresponds to approximately 0.01 to 90% by weight of the total weight of the final formulation, respectively. The total amount of active ingredients in the mixed compositions is in the range of about 0.01 to 90% by weight, preferably about 0.05 to 20% by weight, more preferably about 0.5 to 15% by weight of the total weight of the final formulation.

Agrochemically active substances that are liquid at ambient temperature or that melt at or near room or ambient temperature (e.g., etafenprox), etc. may be dissolved or dispersed in solvents such as high boiling point solvents (e.g., phenyloxylethyl, di-2) prior to use. -ethylhexyl adipate, 2-ethylhexylphenylphosphate, etc.).

The compositions of the present invention may be used in combination with acaricides, nematocides, herbicides, growth hormones, plant growth regulators, synergists, attractants, repellents, pigments, fertilizers, manure and the like.

When the pesticide of the present invention is in the form of a wetting powder, it can be diluted, for example, 30-4000 times, preferably 300-3000 times, with water before use. The final concentration of the active component is usually in the range of 5-1000 parts per million (md). A better final concentration of the α-unsaturated amine derivative or its salt is in the range of 10-300 md.

Amounts used can vary over a wide range depending on the season, location and use, and so on. factor. Preferably, the pesticide of the present invention is used in such a way that the amount of active component (i.e., α-unsaturated amine derivative and / or its salt) is in the range of 10-500 g, more preferably 50-300 g per ten ares.

The compositions of the invention are used, for example, to directly spray the leaves or plant stems and to treat the soil at the roots or seedlings in boxes.

The compositions may be effective in combating or killing harmful insects and insects parasitizing on plants such as rice, vegetable crops (e.g., cabbage, Japanese cabbage (Brassica rapa L. var, amplexi caulis Tnaka and Ono), Japanese horseradish (Raphanus sativus L. var)). hortensis Bekep), cucumbers, potatoes, etc.), fruit trees (such as citrus, pears, etc.), tea, tobacco and the like.

These pests, such as Chilo medinalis, Psedaletia, include pests such as suppressalis, Cnaphalocrocis separata, Mamestra brassicae,

Plutella xylostella, Caloptilla theivora, Aoloxophyes sp .; Coleoptera pests such as Lissorhoptrus oryzophilus, Echinocnemus sguameus, Oulema oryzae, Aulacophora femoralis; pests such as Nephotettix cincticeps, Nilaparvata lugens, Laodelphax striatellus, Sogatella furcifera, Trialeurodes vaporariorum, Bemisia tabaci, Psylla pyricola; aphids such as Aphis gossypii, Myzus persicae, Macrosiphum euphorbiae; pests such as Scirtothrips dorsalis, Thrips pabmi and others.

Examples of such pests include stem fescue (rice fescue, striped rice fern), rice foxtail (rice fever), rice caterpillar, edible bell, cabbage owl, cuckoo moth, pumpkin leaf beetle, green rice cicada, rice delphocides, brown rice grasshopper, small brown grasshopper, white-winged green potato, white-finned pear, pear frog, aphid (tea aphid), peach aphids; peach-potato aphids (potato aphids, tomato aphids), tea thrips, legume thrips and others.

The compositions may be used at insect sites (e.g., at the point of killing or clinging or gathering), as a general protective agent (ie, before infestation) or as a means of destruction (after infestation).

The compositions of the present invention may be used in the methods or working examples described herein.

Preferred compositions of the present invention are DL dusts, granules and wetting powders.

Better DL dust composition includes:

- active substance ((I) α-unsaturated amino derivative and / or its salt, etc.)

solid carrier (filler earth, etc.)

- acidic (phosphoric acid, etc.)

- binding agent (anionic surfactant (Neocol SW-C ™, etc.), etc.), and

- DL material (IP Solvent, etc.).

Better granule compositions include:

- active substance ((I) α-unsaturated amino derivative and / or its salt, etc.)

solid carrier (filler earth, etc.)

- binding agent (dextrin, etc.)

- penetrating agent (anionic surfactant (Toxanone GP-30 ™, etc.), etc., and

- aggregate (mole, etc.).

A better moisturizing powder composition includes:

active substance ((I) α-unsaturated amino derivative and / or its salt, etc.) solid carrier (fuller earth, etc.)

- acid (phosphoric acid, etc.)

dispersant (anionic surfactant (Dixol WK ™, etc.), etc.

Even better DL dust compositions include:

- active substance ((II) α-unsaturated amino derivative and / or its salt, etc.)

solid carrier (filler earth, etc.)

- acid (phosphoric acid, etc.)

- binding agent (anionic surfactant (Neocol SVJ-C ™, etc.), etc., and

- DL material (IP Solvent, etc.).

Even better pellet composition contains:

- active substance ((II) α-unsaturated amino derivative and / or its salt, etc.)

solid carrier (filler earth, etc.)

- acid (phosphoric acid, etc.)

- binding agent (dextrin, etc.)

- penetrating agent (anionic surfactant (Toxanone GP-30 ™, etc.), etc., and

- aggregate (clay, etc.).

Even better moisturizing powder composition contains:

- active substance ((II) α-unsaturated amino derivative and / or its salt, etc.)

solid carrier (filler earth, etc.)

- acid (phosphoric acid, etc.), and

- a dispersing agent (anionic surfactant (Dixol WK ™, etc.), etc.).

The composition of the present invention can inhibit degradation of the anesed amine derivative (I), (II), or a salt thereof, even when stored for prolonged periods and prevent photodegradation in sunlight, even when sprayed in rice and altitude fields. stable, has no harmful effect on crops and is particularly useful in combating, controlling and preventing plant pests or organisms which are harmful to plants.

In addition, the compositions of the present invention may contain other agrochemically active substances which, in prior art formulations, were not capable of mixing with (I), (II) α-unsaturated amino derivatives or their salts.

Moreover, the active ingredients of the compositions of the invention are readily available after use. Another advantage of the compositions of the invention is that they can be readily prepared in an industrial manner.

The pesticide formulations thus obtained are extremely low toxic and stable, harmless and are very good poisonous agricultural chemicals. They can be used in the same way as conventional insecticides and exhibit excellent stability over conventional products.

<td>c</td><td>The following are examples invention.</td><td>finely</td><td>explains</td>

<td></td><td>EXAMPLES</td><td></td><td></td>

<td> 10</td><td colspan="3">The following reference examples, working examples, and test examples illustrate the invention in more detail, but should not be construed as meaning although in a way limiting the invention.</td>

<td> 15</td><td>Reference Example 1</td><td></td><td></td>

<td></td><td>Dl type dust (without solid carrier and without pH adjustment)</td><td>capable</td><td>adsorb</td>

<td> 20</td><td>In 98.25 parts of crushed clay</td><td>powder</td><td>attached</td>

0.25 parts of compound 3, followed by 1.0 parts of liquid paraffin (Driless C ™, hereafter referred to as Driless C ™) and 0.5 parts of white soot, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to give a DL type dust containing compound 3.

reference example

DL type dust (without the ability to adsorb solid carrier and without pH adjustment; mixture with cartilage).

To 96.25 parts of crushed clay powder is added 0.25 parts of Compound 3, followed by 2.0 parts of Cartap, 1.0 part of Driless C ™ and 0.5 parts of white soot, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to obtain a DL-type dust containing 3 compounds and a cartap.

reference example

DL type dust (without solid carrier capable of adsorption and without pH adjustment; mixture with validamycin A)

To 97.95 parts of crushed clay powder is added 0.25 parts of compound 3, followed by 0.3 parts of validamycin A, 1.0 part of Driless C ™ and 0.5 parts of white soot, and the resulting mixture is mixed well with an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL type dusts containing Compound 3 and Validamycin A.

reference example

DL type dust (without solid carrier capable of adsorbing and without pH adjustment; blend with ferrimon and phthalide)

To 94.75 parts of crushed clay powder was added 0.25 parts of Compound 3, followed by 2.0 parts of ferrimon, 1.5 parts of phthalide, 1.0 part of Driless C ™ and 0.5 parts of white soot, and the resulting mixture was mixed well. with automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL-type dusts containing Compound 3, ferrimon and phthalide.

reference example

Granules (without solid carrier capable of adsorption)

To 93.0 parts of crushed clay powder is added 1.0 part of compound 3, followed by 5.0 parts of dextrin and 1.0 part of 85% phosphoric acid, and the resulting mixture is mixed well. Add water to the mixture and mix well when wet. The wetted mixture is granulated with a vibratory granulator (sieve diameter 1.0 mm) to obtain wet products. The products are dried and sieved from 10 to 32 mesh pellets.

reference example

Moisturizing powder (without a solid carrier that can adsorb and do not adjust pH)

To 82.0 parts of clay was added 10.0 parts of compound 3, followed by 5.0 parts of Njukalgen BX-C ™ (Takemoto Yushi KK, Japan) and 3.0 parts of white soot, and the resulting mixture was thoroughly mixed by an automatic mortar. The mixture is pulverized in a fine mill to give a wetting powder containing the compound of Compound 3.

reference example

DL-type dust (no solid carrier capable of adsorption and no pH adjustment) compound (20.0 parts) is dissolved in 80.0 parts water (pH adjusted to 3.0). The solution (1.25 parts) is mixed well with 5.0 parts of crushed clay powder. To the 6.25 parts of the resulting mixture is added 7.25 parts of crushed clay powder, 1.0 part of Driless C ™, 0.5 parts of white carbon and 15.0 parts of anhydrous gypsum, and the mixture is well mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to give DL type dust containing Compound 3.

reference example

DL type dust

To 93.25 parts of crushed clay powder is added 0.25 parts of Compound 3, followed by 1.0 parts of Driless ™, 5.0 parts of fuller earth and 0.5 parts of white soot, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized into a powder by a Bantam mill to produce DL-type dust containing Compound 3.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). The solution (1.25 parts) is well mixed with the filler earth until homogeneous. To the 6.25 parts of the resulting mixture is added 77.25 parts of crushed clay powder, followed by 1.0 parts of Driless C ™, 0.5 parts of white soot and 15.0 parts of anhydrous gypsum, and the mixture is thoroughly mixed using an automatic mortar. The mixture is then pulverized in a Bantam mill to give DL type dust containing Compound 3.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). The solution (1.25 parts) is mixed well with 5.0 parts of fuller earth, 77.25 parts of clay powder, 1.0 part of Driless C ™, 0.5 part of white soot and 15.0 part of anhydrous gypsum to form a mixture. mix well with an automatic mortar. The mixture is then pulverized in a Bantam mill to obtain DL type dusts containing 3 compounds.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). The solution (1.25 parts) was mixed well with 5.0 parts of sepiolite (Aidplus, Takeda Chemical Industries Ltd) until homogeneous. To

6.25 parts of the resulting mixture are added 77.25 parts of crushed clay powder, followed by 10 parts of Driless C ™, 0.5 parts of white soot and 15.0 parts of anhydrous gypsum, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL-type dust containing Compound 3.

An example

DL-type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). The solution (1.25 parts) is mixed well with 5.0 parts of β-cyclodextrin to become homogeneous. To 6.25 parts of the resulting mixture is added

77.25 parts crushed clay powder followed by 1.0 parts

Driless C ™, 0.5 parts white soot and 15.0 parts anhydrous plaster, and the resulting mixture is well blended with an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL-type dust containing Compound 3.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). The solution (1.25 parts) is mixed well with 5 parts of a fuller earth automatic mortar to become homogeneous. To the 6.25 parts of the resulting mixture is added 76.95 parts of crushed clay powder, followed by 0.3 parts of validamycin A, 1.0 part of Driless C ™, 0.5 parts of white soot and 15 parts of anhydrous gypsum and mix well with automatic mortar. The mixture is then pulverized into a Bantam mill to obtain DL type dusts containing Compound 3 and Validamycin A.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). The solution (1.25 parts) was mixed well with 5.0 parts of a fuller mortar to obtain a homogeneous mixture of 75.25 parts of earth automatic to 6.25 parts of the resulting crushed clay powder, followed by 2.0 parts of cartap, 1.0 parts Driless C ™, 0.5 parts white soot and 15.0 parts anhydrous gypsum, and the resulting mixture is well blended with an automatic mortar. The mixture is then pulverized in a Bantam mill to obtain DL type dusts containing Compound 3 and Carthage.

An example

The DL-type dust (process 1) compound (15.0 parts) is mixed and dissolved in 55.0 parts of water and 30.0 parts of phosphoric acid. The solution (1.75 parts) mixes well with 5.0 parts of a fuller earth automatic mortar. 1, 6.25 parts of the resulting mixture are added 76.75 parts of crushed clay powder, followed by 1.0 part IP Solvento ™, 0.5 parts white soot and 15.0 parts anhydrous gypsum, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL-type dust containing Compound 3. % by weight of DL-type dust suspension measured by pH meter, pH 4.5.

An example

DL type dust (process 2) compound (20.0 parts) is dissolved in 80.0 parts water. The aqueous solution (1.25 parts) is added to a premixed mixture of phosphoric acid (0.5 parts) and fuller earth (5.0 parts). The resulting mixture is mixed well with an automatic mortar until homogeneous. The mixture was then dried at 60 ° C under vacuum. To the 5.75 parts of the dried mixture is added 77.75 parts of crushed clay powder, followed by 1.0 part of IP Solvento ™, 0.5 parts of white soot and 15.0 parts of anhydrous gypsum, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to give DL type dust containing Compound 3. 10% DL type dust suspension measured with a pH meter, pH 4.5.

An example

DL-type dust (process 1) compound (2.0 parts) is dissolved in 58.0 parts of water (previously adjusted to pH 3 with phosphoric acid as measured by pH meter). The solution (60.0 parts) was mixed with 40.0 parts of fuller earth until homogeneous and the resulting mixture was dried in a disintegrating dryer (L-8, Ochokavara Kakouki KK, Japan). To 5.5 parts of the dried mixture is added 91.5 parts of crushed clay powder, followed by 0.5 parts of IP Solvento ™, 0.5 parts of ultra-pure alumina microparticles and 2.0 parts of Neocolch SW-C ™, and the resulting mixture is well mix with an automatic mortar. The mixture is then pulverized in a Bantam mill to give DL type dust containing Compound 3.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). Solution (1.25 parts) well ground auto Mix 6.25 parts of the resulting crushed clay with 5.0 parts of fuller mortar to homogeneously add 77.25 parts of powder, then 1.0 part of IP Solvento ™, 0 , 5 parts white soot and 15.0 parts anhydrous plaster, and the resulting mixture is thoroughly mixed with an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL type dusts containing Compound 1.

An example

DL type dust (process 1) compound (20.0 parts) is dissolved in 80.0 parts water (previously adjusted to pH 3 with phosphoric acid, measured by pH meter). To 1.25 parts of the solution is added 5.0 parts of fuller earth followed by 77.25 parts of crushed clay powder, 1.0 part of Driless C ™, 0.5 parts of white soot and 15.0 parts of anhydrous gypsum, and the resulting mixture is well mix with an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL-type dust containing 1 compound.

An example

The DL-type dust (process 1) compound (15.0 parts) is mixed and dissolved in 55.0 parts of water and 30.0 parts of phosphoric acid. The solution (1.75 parts) mixes well with 5.0 parts of a fuller earth automatic mortar and becomes homogeneous. To

To 6.25 parts of the resulting mixture is added 77.25 parts of crushed clay powder followed by 1.0 part IP Solvento ™, 0.5 parts white soot and 15.0 parts anhydrous gypsum, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL type dusts containing Compound 1. 10% DL type dust suspension as measured by pH meter, pH 4.5.

An example

DL type dust (process 2) compound (20.0 parts) is dissolved in 80.0 parts water. The aqueous solution (1.25 parts) is added to a well-mixed mixture of phosphoric acid (0.5 parts) and fuller earth (5.0 parts). The resulting mixture is mixed well with an automatic mortar until homogeneous. The mixture was then dried at 60 ° C under vacuum. to

5.75 parts of the dried mixture are added 77.75 parts of crushed clay powder, followed by 1.0 part IP Solvento ™, 0.5 parts white soot and 15.0 parts anhydrous gypsum, and the resulting mixture is thoroughly mixed by an automatic mortar. The mixture is then pulverized in a Bantam mill to produce DL type dusts containing Compound 1. A 10% DL type dust suspension, measured by pH meter, showed a pH of 4.4.

An example

Granule (Process 3)

To 83.00 parts of crushed clay powder is added 10.0 parts of fuller earth, followed by 1.0 part of compound 3, 5.0 parts of dextrin and 1.0 part of 85% phosphoric acid, and the mixture is thoroughly mixed. water is added to the mixture and the moistened mixture is thoroughly mixed. The wetted mass is granulated with a vibratory granulator (sieve diameter 1.0 mm) to form a secret product. The products are dried and sieved with 10 to 32 mesh pellets. The granules are ground to a powder and 10% of their suspension, measured by pH meter, has a pH of 3.1.

An example

Granule (process 4)

To 83.00 parts of crushed clay powder add 10.0 parts of a fuller earth, followed by 1.0 part of compound 3, 5.0 parts of dextrin and an aqueous solution containing 1.0 part of 85% phosphoric acid, and the resulting mixture is mixed very well . Water is added to the mixture and the wet mixture is thoroughly mixed. The wet mass is granulated with a vibratory granulator (sieve diameter 1.0 mm) to form sensitive products. The products are dried and sieved with 10 to 32 mesh pellets. The pellets are pulverized and the pH of the suspension is adjusted to 3.0 with a pH meter.

An example

Moisturizing powder (process 4) is crushed

To 77.0 parts of a fuller earth is added 10.0 parts of Compound 3, followed by 5.0 parts of 85% phosphoric acid, 5.0 parts of Njukalgen BX-C ™ (Takemoto Yushi KK, Japan) and 3.0 parts of white soot, and the resulting mixture is well blended with an automatic mortar. Mixture of powder in a fine grinding mill to obtain a wetting powder.

An experimental example

Investigation of storage stability

Each blended preparation obtained from 1 to 16

Samples and Reference Examples 1-8 (20 g each) were stored for a set period of time at a temperature also determined in a paper pack for powder materials, a paper pack for granules, or an aluminum pack for a wetting powder. Samples were then taken from the packages. The sample is accurately measured (10 mg of a-unsaturated amino derivative or its salts) and extracted by shaking for 30 minutes with 40 ml of a mixture of acetonitrile: 0.5 M water. KH₂PO₄ - 50/50 (v / v).

The content of α-unsaturated amino derivatives or their salts in the extract was determined by high performance liquid chromatography (HPLC, column; Nucleosyl 10-C).₁₈,

Gaschro, Industries, KK, Japan; eluent:

acetonitrile: 0.5 M vand. KH₂PO₄ - 50/50 (v / v).

The percent degradation (%) of α-unsaturated amino derivatives or their salts was calculated using the formula:

Residue of α-unsaturated amino derivatives or their salts in the preparations after a fixed period of time at the determined temperature of α-unsaturated amino derivatives or their = (1-) x100 salts Dissolution of α-unsaturated amino derivatives or their (%) salts immediately after production

The results are shown in Tables 1-3.

Table Shelf life of α-unsaturated amino derivatives or their salts in single or mixed DL type dusts

<td>Under investigation</td><td>Stabilizer</td><td>α-Unsaturated</td><td>of amino derivatives; or</td>

<td>preparation</td><td></td><td>of their salts</td><td>decay through 2</td>

<td></td><td></td><td>months,</td><td>At 40 ° C</td>

<td>1 Example</td><td>Fuller Land</td><td></td><td> 1,5%</td>

<td>2 Example</td><td>Fuller Land</td><td></td><td> 1,7%</td>

<td>Example 3</td><td>Sepiolite</td><td></td><td> 7,3%</td>

<td>Example 4</td><td>α-cyclodextrin</td><td></td><td> 3,3%</td>

<td>5 Example</td><td>Fuller Land</td><td></td><td> 1, 6%</td>

<td>6 Example</td><td>Fuller Land</td><td></td><td> 1,7%</td>

<td>Example 7</td><td>Fuller Land</td><td></td><td> 1,2%</td>

<td>8 Example</td><td>Fuller Land</td><td></td><td> 3,2%</td>

<td>Control:</td><td></td><td></td><td></td>

<td>Reference 1</td><td></td><td></td><td></td>

<td>example</td><td>There is no</td><td></td><td> 21,6%</td>

<td>Reference 7</td><td>Shredded</td><td></td><td></td>

<td>example</td><td>clay powder</td><td></td><td> 36,3%</td>

<td>Reference 8</td><td>Land of Fuller (without</td><td></td><td></td>

<td>example</td><td>acid)</td><td></td><td> 17,8%</td>

Table Shelf life of α-unsaturated amino derivatives or their salts in granules 5

<td>Under investigation preparation</td><td>Stabilizer</td><td>α-Unsaturated amino derivatives or their salt decomposition over 2 months at 40 ° C</td>

<td>14 Example</td><td>Fuller Land</td><td> 4,1%</td>

<td>Control:</td><td></td><td></td>

<td>Reference 5</td><td>There is no</td><td></td>

<td>example</td><td></td><td> 17,7%</td>

<td>Table 3</td><td></td><td></td>

<td colspan="2">α-Unsaturated amino derivatives or in moisturizing powder</td><td>l the shelf life of their salts</td>

<td>Under investigation</td><td>Stable-</td><td>α-unsaturated amino derivatives or</td>

<td>preparation</td><td>tori</td><td>decomposition of their salts within 2 months at 40 ° C</td>

<td>16 Example</td><td>Fuller Land</td><td> 1,2%</td>

<td>Control:</td><td></td><td></td>

<td>Reference 6</td><td>There is no</td><td></td>

<td>example</td><td></td><td> 10,3%</td>

An experimental example

Stability studies in photolithic degradation

In the Example and Reference Example 6, the resulting product (1 g) was diluted in 1000 mL water to give a 1000 dilution. The diluted preparation is evenly distributed in a Petri dish (8.6 cm diameter x 2.0 cm height), then dried at 60 ° C for 2 hours.

Two samples are prepared, one exposed to sunlight and the other to darkness.

The sample is exposed to sunlight, then the a-unsaturated amino derivative or its salt is extracted by shaking with 50 ml of acetonitrile: 0.5 M water. KH₂PO₄ - 50/50 (v / v).

The composition of α-unsaturated amino derivatives or their salts is determined by high performance liquid chromatography (HPLC, column; Nucleosyl 10-C₁₈, Gaschro, Industries, KK, Japan; eluent: acetonitrile: 0.5 M water KH₂PO₄ - 50/50 (v / v).

Table: Photo-degradation resistance of α-unsaturated amino derivatives or their salts by spray wetting powder

<td rowspan="2">Test preparation</td><td colspan="2">α-Unsaturated amino derivatives or isolation of their salts through 2</td><td rowspan="2">Fateful indicator</td>

<td>months</td><td>At 40 ° C</td>

<td>16 Example (dark)</td><td></td><td> 96, 1%</td><td> 100,0%</td>

<td>16 Example (sunlight)</td><td></td><td> 76, 9%</td><td> 88,3%</td>

<td>Control: Reference 6 example (dark)</td><td></td><td> 97,5%</td><td> 100,0%</td>

<td>Reference Example 6 (sunlight)</td><td></td><td> 33,5%</td><td> 34,3%</td>

Isolation: Degree of resolution of α-unsaturated amino derivatives or their salts with respect to the amount added.

Residual level: A certain amount of the remaining α-unsaturated amino derivatives or their salts in preparations stored in the sunlight compared to preparations stored in the dark (= 100).

An experimental example

Adsorption study

Weigh accurately 500 mg of compound 3, transfer to a 100 ml glass measuring cylinder and dissolve in purified water (pH adjusted to 3 or 6) to give a defined volume.

Weigh accurately 500 mg of fuller earth and transfer to a 100 ml Erlenmeyer flask. Transfer the specified solution into a Erlenmeyer flask with a 40 ml graduated pipette. The resulting suspension was stirred at 26 ° C for 3 hours.

Fuller ground is centrifuged at 3000 rpm and the concentration of compound in the washed layer is determined by high performance liquid (HPLC / column; Nocleoside 10-C).₁₈, tries KK, Japan; eluent: acetonitrile: 0.5 M wt. KH₂PO₄ - 50/50 (v / v). The amount of compound 3 embedded in fuller earth is evaluated by observation.

chromatography Gaschro, Indus5 Table

30 'Adsorption of α-unsaturated amino derivatives or their salts on fuller earth pH Adsorption of α-unsaturated amino derivatives or their _ salts on fuller earth (romol / g) _

42.6 χ 10 '²10.9 χ 10 '²

The adsorbed amount is calculated using the formula:

Adsorption = (Compound 3 in aqueous solution - Compound 3 in the washed layer) / amount of fuller earth added.

An experimental example

Adsorption study

The amount of adsorbed compound in the crushed clay powder at pH 3.0 was measured in the same manner as in Experiment 3.

Table Adsorption of α-unsaturated amino derivatives or their salts in crushed clay powder pH Adsorption of α-unsaturated amino derivatives or their salts in crushed clay powder (mmol / g)