JPH0525144A - Uracil derivative and noxious organism controlling agent - Google Patents

Abstract

PURPOSE:To provide a new uracil derivative having excellent insecticidal and miticidal activity against various agricultural vermin and spider mites and giving nearly no adverse effect on mammals, fishes and beneficial insects. CONSTITUTION:The compound of formula I [R<1> is H, alkyl, benzyl, phenyl, etc.; R<2> is H, halogen, alkyl, SH, OH, alkoxy, CN, NH2, etc.; Z<1> and Z<2> are O, S or NH; A is group of formula II (X is halogen, alkyl, alkoxy, NH2, NO2, etc.; (l) is 0-5), naphthyl, furyl, thienyl, etc., and B is group of formula III (Y<1> is halogen, alkyl, alkenyl, NO2, CN, etc.; (m) is 0-5) or A is haloalkyl, halogen, CN, NO2, etc., and B is group of formula IV (Y<2> is halogen, alkyl, alkoxy, etc.; (r) is 3-5)], e.g. 3-[4-(2-pyrimidyloxy)phenyl]-6-(2-chlorophenyl)-2,4(1H,3H)- pyrimidine-dione.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel uracil derivative and a pest control agent containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, some patents and literatures have described uracil compounds. Journal of
American Chemical Society (J.Amer.Chem.So
c.), 58, 299 (1935), 3,6-diphenyluracil and 3-phenyl-6- (3-bromo-4-
Methoxyphenyl) uracil is described.

Further, the chemical abstract (Chem.A
b.), 52, 6364h (1958), 3,6-diphenyluracil is described. However, the above literature does not show any activity of these compounds against organisms. or,
U.S. Pat. Nos. 3,580,913, 3,869,457 and 3,981,715 disclose uracil compounds in which the 6-position is a trifluoromethyl group and the 3-position is an unsubstituted or substituted phenyl group. Is limited to 2, and a phenyl group having 3 or more substituents is not described. Further, the above patent does not show any activity of these compounds for controlling pests.

Further, Japanese Patent Laid-Open Publication No. 61-221178,
Sho 63-41466, Sho 63-107967, International Publication Number WO88-102
Nos. 54, WO89-02891 and WO89-03825 disclose that the 6-position is a hydrogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ fluoroalkyl group, and the 3-position is three at the 2, 4, 5 positions. Although the uracil compound which is a substituted phenyl group is described, the substituent at the 5-position of the phenyl group is limited to the substituents linked by an oxygen atom or a carbonyl group. Further, the above patent does not show any activity of these compounds for controlling pests.

[0005]

Due to the long-term use of insecticides, pests have acquired resistance in recent years, making it difficult to control them with conventional insecticides. In addition, some insecticides are highly toxic, and some are perturbing the ecosystem due to persistence. Therefore, the development of new insecticides with low toxicity and low residue is always expected.

[0006]

The present invention has the general formula [I]

[0007]

[Chemical 12]

In the formula, R ¹ is a hydrogen atom, a C _{1 to} C ₄ alkyl group, a C _{2 to} C ₄ alkenyl group, a C _{2 to} C ₄ alkynyl group, and a C _{1 to} C ₄
Haloalkyl groups, C ₂ -C ₄ alkoxyalkyl group, formyl group, C ₂ -C ₆ alkylcarbonyl group, C ₂ -C ₆ alkoxycarbonyl group, C ₃ -C ₆ alkoxycarbonylalkyl group, C ₂ -C ₆ cyanoalkyl Represents a group, a benzyl group, a phenyl group, an alkali metal or an alkaline earth metal, R ² is a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ haloalkyl group, a C _{1 to} C ₄ hydroxyalkyl group, C ₂ -C ₄ alkoxyalkyl group, C ₂ -C ₄ alkylthioalkyl group,
Thiol group, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ alkylsulfinyl group, C ₁ -C ₄ alkylsulfonyl group, C ₁ -C ₄ haloalkylthio group, C ₁ -C ₄ haloalkylsulfinyl group, C ₁ ~ C ₄ haloalkylsulfonyl group, hydroxy group,
C _{1 to} C ₄ alkoxy group, C _{1 to} C ₄ haloalkoxy group, formyl group, cyano group, nitro group, amide group or thiocyanate group is shown, and Z ¹ and Z ² are each independently an oxygen atom, a sulfur atom or Represents an imino group, A is

[0009]

[Chemical 13]

{Where X is a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkylthio group,
C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ haloalkoxy group, C ₁ ~
C _{4 represents a} haloalkylthio group, an amino group, a cyano group, or a nitro group, and 1 represents an integer of 0 to 5 (provided that in the case of 2 to 5, X may be the same or different). }, An unsubstituted or optionally substituted naphthyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, Pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group (however, the optionally substituted substituents are a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkylthio group). A group, a C _{1 to} C ₄ haloalkyl group, a C _{1 to} C ₄ haloalkoxy group, a C _{1 to} C ₄ haloalkylthio group, an amino group, a cyano group or a nitro group, and when the number of the substituents is 2 or more, The substituents may be the same or different), a C ₁ -C ₆ haloalkyl group containing at least one fluorine atom, a halogen atom, a cyano group, Toromoto, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ ~ C ₆ haloalkylsulfonyl group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ haloalkoxy group or C _{2 to} C ₆ alkoxycarbonyl group, wherein A is

[0011]

[Chemical 14]

(Wherein X and l have the same meanings as described above), an unsubstituted or optionally substituted naphthyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thiazolyl group, isothiazolyl group. In the case of a group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, a pyridyl group, a pyridazyl group, a pyrimidyl group or a pyrazyl group, B is

[0013]

[Chemical 15]

[Wherein Y ¹ is a halogen atom, a C _{1 to} C ₆ alkyl group, a C _{2 to} C ₆ alkenyl group, a C _{2 to} C ₆ alkynyl group, a C ₃
To C ₆ cycloalkyl group, C _{1 to} C ₆ haloalkyl group, C _{2 to} C ₆
Haloalkenyl group, C ₂ -C ₆ haloalkynyl group, C ₃ -C ₆ halocycloalkyl group, C ₂ -C ₆ cyanoalkyl group, C ₁ -C ₆
Hydroxyalkyl group, C ₂ -C ₆ carboxyalkyl group,
C ₁ -C ₆ alkoxy group, C ₂ -C ₆ alkenyloxy group, C ₂ ~
C ₆ alkynyloxy group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₆ haloalkoxy group, C ₂ -C ₆ haloalkenyloxy group, C ₂ -C ₆ haloalkynyl group, C ₃ -C ₆ halo cycloalkoxy group, C ₄ -C ₇ halocycloalkyl alkoxy group, C ₁ -C ₆ alkylthio group, C ₂ -C ₆ alkenylthio group, C ₂ -C ₆ alkynylthio, C ₃ -C ₆ cycloalkylthio group , C _{1 to} C ₆ haloalkylthio group, C _{1 to} C ₆ alkylsulfinyl group, C _{2 to} C ₆ alkenylsulfinyl group, C _{2 to} C ₆
Alkynylsulfinyl group, C ₃ -C ₆ cycloalkyl alkylsulfinyl group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ ~
C ₆ alkylsulfonyl group, C ₂ -C ₆ alkenylsulfonyl group, C ₂ -C ₆ alkynylsulfonyl group, C ₃ -C ₆ cycloalkylsulfonyl group, C ₁ -C ₆ haloalkylsulfonyl group,
C ₂ -C ₆ alkoxyalkyl group, C ₂ -C ₆ alkoxyalkoxy, C ₂ -C ₆ haloalkoxyalkyl group, C ₂ -C ₆ haloalkoxy alkoxy group, C ₂ -C ₆ alkylthioalkyl group, C ₂ ~ C ₆ alkylthioalkoxy group, C ₃ -C ₆ alkoxycarbonylalkyl group, C ₃ -C ₆ alkylcarbonyl group, C ₂ -C ₆ alkoxycarbonyloxy group, C ₂ ~
C ₆ alkylcarbonyloxy group, C ₂ -C ₆ alkylcarbonyl group, C ₃ -C ₆ alkenylcarbonyl group, C ₃ -C ₆ alkynyl group, C ₄ -C ₇ cycloalkylcarbonyl group, C ₂ -C ₆ haloalkyl carbonyl group, C ₂ -C ₆ alkoxycarbonyl group, C ₂ -C ₆ haloalkoxycarbonyl groups,
C ₃ -C ₆ alkoxycarbonylalkoxy group, a nitro group,
Cyano group, hydroxy group, carboxyl group, thiocyanate group, isothiocyanate group, C ₂ -C ₆ thiocyanate alkyl group, C ₁ -C ₆ alkylsulfonyloxy group, C ₂ ~
C ₆ alkylthiocarbonyl group, amino group (-NR ³ R ⁴ ), aminocarbonyl group (-CONR ³ R ⁴ ), aminocarbonyloxy group
(-OCONR ³ R ⁴ ), amide group (-NR ³ COR ⁴ ), alkoxycarbonylamino group (-NR ³ CO ₂ R ⁴ ), aminosulfonyl group (-SO ₂ N
R ³ R ⁴ ), thioamide group (-NR ³ CSR ⁴ ), methylenedioxy group, halomethylenedioxy group, ethylenedioxy group, haloethylenedioxy group, trimethylsilyl group or

[0015]

[Chemical 16]

{However, W is

[0017]

[Chemical 17]

Or

[0019]

[Chemical 18]

(However, R ³ and R ⁴ are each independently a hydrogen atom, a C _{1 to} C ₆ alkyl group, a C _{2 to} C ₆ alkenyl group, and a C _{2 to} C ₆
Alkynyl group, C ₁ -C ₆ haloalkyl group, C ₂ -C ₆ haloalkenyl group, C ₂ -C ₆ haloalkynyl group, C ₂ -C ₆ alkylcarbonyl group, C ₂ -C ₆ alkoxycarbonyl group, a phenyl group or A benzyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group, a cyano group or a phenyl group, and q
Represents an integer of 0 to 2. ), N is an integer of 0 or 1, Ar is an unsubstituted or optionally substituted phenyl group, naphthyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thiazolyl group, isothiazolyl Group, oxazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, quinolyl group or quinoxalyl group (however,
As the substituent which may be substituted, a halogen atom, a cyano group, a nitro group, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ haloalkyl group, a C _{1 to} C ₄ alkoxy group, and a C _{1 to} C ₄ haloalkoxy group. , C _{1 to} C ₄ alkylthio group, C _{1 to} C ₄ haloalkylthio group, C _{1 to} C ₄ alkylsulfonyl group, C _{1 to} C ₄ haloalkylsulfonyl group, C _{2 to} C ₄ alkoxycarbonyl group, carboxyl group, amino group , Mono C ₁ -C ₄ alkylamino group, di
C ₁ -C ₄ alkylamino group, a phenyl group, a benzyl group, a methylenedioxy group or halo methylenedioxy group, the substituent when the substituent is two or more may be different even in the same ) Is shown. }, And m is an integer of 0 to 5 (provided that Y ¹ may be the same or different in the case of 2 to 5). ], An unsubstituted or optionally substituted naphthyl group, a furyl group, a thienyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a thiazolyl group,
Isothiazolyl group, oxazolyl group, isoxazolyl group, thiadiazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, quinolyl group, quinoxalyl group, benzofuryl group, benzothienyl group, indolyl group, benzoxazolyl group Group or benzothiazolyl group (provided that the substituent which may be substituted is a halogen atom, a cyano group, a nitro group, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ haloalkyl group, a C ₁
-C ₄ alkoxy, C ₁ -C ₄ haloalkoxy groups, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ haloalkylthio group, C ₁ -C ₄ alkylsulfonyl group, C ₁ -C ₄ haloalkylsulfonyl group,
C ₂ -C ₄ alkoxycarbonyl group, carboxyl group, amino group, mono C ₁ -C ₄ alkylamino group, di C ₁ -C ₄ alkylamino group, phenyl group, phenoxy group or benzyl group, wherein the substituent is 2 And the number of the substituents may be the same or different, and A represents a fluorine atom.
FOB inclusive C ₁ -C ₆ haloalkyl group, a halogen atom, a cyano group, a nitro group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁
-C ₆ haloalkylthio group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ -C ₆ haloalkylsulfonyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group or a C ₂ -C ₆ alkoxycarbonyl group In case of

[0021]

[Chemical 19]

{However, Y ² is a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ haloalkyl group,
C ₁ -C ₄ haloalkoxy groups, C ₁ -C ₄ alkylthio group, C ₁ ~
C ₄ haloalkylthio group, C ₁ -C ₄ alkylsulfinyl group, C ₁ -C ₄ haloalkylsulfinyl group, C ₁ -C ₄ alkylsulfonyl group, C ₁ -C ₄ haloalkylsulfonyl group, a sulfonamido group, C ₂ -C ₄ alkenyl group, C ₂ -C ₄ haloalkenyl group, amino group, mono C ₁ -C ₄ alkylamino group, di
C _{1 to} C ₄ alkylamino group, C _{2 to} C ₆ alkoxyalkoxy group, C _{2 to} C ₆ alkoxycarbonyl group, cyano group or nitro group, r is an integer of 3 to 5 (provided that Y ² is the same. May be present or different, and in the case of a tri-substituted product at the 2,4,5-position with r = 3, the substituent Y ^{2 at the} 5-position is a C ₁ -C ₄ alkoxy group, C ₁ -C ₄ haloalkoxy. Group, a C ₂ -C ₆ alkoxyalkoxy group, a C ₂ -C ₆ alkoxycarbonyl group), and A is a phenyl group or 3-
The present invention relates to a uracil derivative represented by the formula: bromine-4-methoxyphenyl group and excluding the case where B is a phenyl group, and a pest control agent containing one or more of the derivatives as an active ingredient.

In the present invention, the pest control agent means especially a pest control agent. The compounds of the present invention are effective against various harmful pests at extremely low drug concentrations. As the pests, for example, green leafhoppers, brown planthoppers, green peach aphids, Aphis moss, Agricultural insect pests such as Spodoptera litura, Plutella xylostella, spider mites, mandarin mites, mosquito mites, etc.
Hygiene pests such as housefly, German cockroach, ants, fleas and lice, storage pests such as weevil, stag beetle, stag beetle, house pests such as termites, livestock pests such as mites, fleas and lice. That is, the compound of the present invention, Orthoptera, hemiptera, Lepidoptera, Coleoptera,
It can effectively control pests of Hymenoptera, Diptera, Termites, and mites and lice at low concentrations. On the other hand, it was found that the compound of the present invention is a very useful compound having almost no adverse effect on mammals, fish, crustaceans and beneficial insects, and completed the present invention.

Next, a method for producing the compound of the present invention will be described. The compound of the present invention is a novel uracil derivative. The synthesis method is, for example, Comprehensive Heterocyclic C
The uracil skeleton can be synthesized with reference to the synthetic method described in Hemistry, Vol. 3, p. 57 (1984) and the like. The manufacturing method including the above method will be specifically described.

[0025]

[Chemical 20]

[0026]

[Chemical 21]

[0027]

[Chemical formula 22]

[0028]

[Chemical formula 23]

[0029]

[Chemical formula 24]

[0030]

[Chemical 25]

[0031]

[Chemical formula 26]

In the formulas (methods A to K), R ¹ , R ² , A,
B, Z ¹ and Z ² have the same meanings as described above, R ⁷ and R ⁸ each independently represent a C _{1 to} C ₆ alkyl group, a benzyl group or a phenyl group, and R ⁹ represents C _{1 to} C ₆ Alkyl group or C ₁ ~
Indicates C ₆ haloalkyl group, R ^{1 0} represents a halogen atom, a nitro group, or a thiocyanate group, R ¹¹ represents a C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl group, L ¹ is a halogen atom, methane It shows a good leaving group such as a sulfonate group, a p-toluenesulfonate group, or a C ₁ -C ₄ alkylsulfate group, and L ² and L ³ are each independently a halogen atom, a hydroxy group, or C ₁ -C _4. Represents an alkoxy group, X ¹ represents a chlorine atom or a bromine atom, X ² represents a fluorine atom, a base atom, a bromine atom or an iodine atom, M ¹ is a sodium atom,
Represents a potassium atom or a copper atom, M ² and M ³ each independently represent a sodium atom or a potassium atom,
Z ³ represents an oxygen atom or a sulfur atom, and hal represents a chlorine atom or a bromine atom. Further, formula [VII], formula [IX], formula [XIX], formula [XXI], formula [XXII], formula [XXIII], formula [XXIV], formula [XXV], formula [XXVI], formula [XXVII] , [XXVIII], [XXIX], [XXX], [XXXII] and [XXXIII] are the compounds of the present invention.

Method A is a method suitable for the synthesis of R ² as a hydrogen atom or a C ₁ -C ₄ alkyl group. The starting material of formula [II] is the journal of heterocyclic chemistry (JH
eterocyclic Chem.), vol. 9, p. 513 (1972) and the like, and can be synthesized by a known method. In step 1, the compound of formula [II] can be easily obtained in good yield by reacting the compound of formula [II] with ammonia or ammonia acetate in the presence of acetic acid in the presence of acetic acid.

In step 2, the compound of the formula [III] and the iso (thio) cyanate of the formula [IV] or the (thio) carbamic acid ester of the formula [V] are added in the presence of a base in an inert solvent. By reacting, the compound of the present invention of the formula [VII] can be obtained without isolating the intermediate [VI]. Examples of the base used include alkali metal alkoxides such as sodium ethoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, or sodium hydride. . As the solvent, lower alcohols such as methanol and ethanol, benzene,
Aromatic hydrocarbons such as toluene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and 1,2-diethoxyethane, halogenation of dichloromethane, 1,2-dichloroethane, etc. Examples thereof include hydrocarbons, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, and mixed solvents thereof. Generally, sodium alkoxide (R ⁷ ONa) is used as a base in the same alcohol (R ⁷ OH) solvent as R ⁷ of the formula [III], or hydrogenated as a base in a tetrahydrofuran, dimethylformamide or dimethylsulfoxide solvent. Preference is given to using sodium. The reaction temperature can be set to any temperature from -30 ° C to the reflux temperature of the reaction mixture.

In step 3, the compound of formula [VII] and the compound of formula [VIII] are reacted in the presence of a base in an inert solvent to give the compound of the present invention of formula [IX]. . When R ¹ is a C _{1 to} C ₄ alkyl group, a C _{2 to} C ₄ alkenyl group, a C _{2 to} C ₄ alkynyl group or a C _{2 to} C ₄ alkoxyalkyl group, as R ¹ -L ^{1 in} formula (VIII) It is preferable to use halides such as chloride and bromide.
When R ¹ is a C ₁ -C ₄ alkyl group, dialkyl sulfate (R
¹ ₂ SO ₄ ) is also suitable. The base used is preferably an alkali metal alkoxide such as sodium ethoxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or sodium hydride. As the solvent, water, lower alcohols such as ethanol, ethers such as 1,2-dimethoxyethane and tetrahydrofuran, dimethylformamide or dimethylsulfoxide are preferable.
The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but is preferably 0 ° C to 30 ° C. When R ¹ is formyl, R ¹ -L ¹ is formic acid halide, and when it is a C ₂ -C ₆ alkylcarbonyl group, R ¹ -L ¹ is C ₂ -C ₆ alkanoic acid halide or anhydride, C ₂ preferably, in the case of -C ₆ alkoxycarbonyl group using a C ₂ -C ₆ alkyl chloroformate or bromo formate as R ¹ -L ^1. Sodium hydride is preferred as the base used. However, in the case of introducing a C ₂ -C ₆ alkylcarbonyl group with an acid anhydride can be carried out the reaction without using a base. The solvent is preferably dimethylformamide or dimethylsulfoxide. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but it is preferably carried out at 0 ° C to 30 ° C.

Alkylation of compounds of formula [VII] where Z ¹ is a sulfur atom usually produces a mixture of N- and S-alkylated products. Desired N-C ₁ ~C ₄ alkyl -, N-C ₂ ~C ₄ alkenyl -, N-C ₂ ~C ₄ alkynyl -
Alternatively, the N—C ₂ -C ₄ alkoxyalkyl compound can be easily isolated from such a mixture by a conventional method such as column chromatography.

Method B is characterized in that various substituents other than a hydrogen atom can be introduced as R ¹ before the formation of the uracil ring. In step 1, a compound of formula [XI] can be obtained by reacting a compound of formula [II] with various amines of formula [X] in the presence of an acid catalyst. The acid used is preferably acetic acid or trifluoroacetic acid. In step 2, a compound of the formula [XI] is reacted with a compound of the formula [XI] and an iso (thio) cyanate of the formula [IV] or a (thio) carbamic acid ester of the formula [V] in the presence of a base. The compound of the present invention of formula [IX] can be obtained without isolation of the intermediate of. Conditions such as a base, a solvent and a reaction temperature used in this step are almost the same as those in Step 2 of Method A.

Method C is an intermediate [VI] in step 2 of Method A.
Is another method of synthesizing. In step 1, the formula [II]
The compound of formula [VI] can be obtained by reacting the compound of formula (X) with (thio) ureas of formula [XIII] in the presence of an acid catalyst in an inert solvent. As the acid catalyst used, strong mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid or phosphoric acids such as orthophosphoric acid and polyphosphoric acid are preferable. As the solvent, benzene, aromatic hydrocarbons such as toluene, carbon tetrachloride, halogenated hydrocarbons such as chlorobenzene or 1,2-dimethoxyethane, 1,
Ethers such as 4-dioxane are preferred. The reaction temperature is
Although any temperature from 20 ° C to the reflux temperature of the reaction mixture can be set, it is preferable to carry out at the reflux temperature.

In step 2, the compound of formula [VI] is cyclized in the presence of a base in an inert solvent to give a compound of formula [VII]
The compound of the present invention can be obtained. The conditions used in this step, such as the base, the solvent, and the reaction temperature, are the same as in step 2 of Method A.
Is almost the same as. Method D is suitable for the synthesis of the compound of the present invention in which Z ¹ is a sulfur atom. The starting material [XIV] can be synthesized by a known method. In Step 1, as in Step 1 of Method A, the compound of the formula [XIV] can be reacted with ammonia acetate in the presence of acetic acid in an inert solvent such as ethanol to obtain the compound of the formula [XV].

In step 2, the compound of formula [XV] is reacted with phosgene or thiophosgene in the presence of a base in an inert solvent to give the compound of the formula [VII]. The base used is preferably an organic base such as triethylamine or pyridine. As the solvent, aromatic hydrocarbons such as benzene and toluene or halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane are preferable. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but is preferably 0 ° C to 30 ° C. Also, 1,1′-thiocarbonyldiimidazole can be used instead of thiophosgene.

Method E is the intermediate [III] in the step 1 of Method A.
] Is another method of synthesizing The compound of the formula [III] can be obtained by reacting the nitrile of the formula [XVI] and the alpha-bromoacetic acid ester of the formula [XVII] in the presence of zinc in an inert solvent. As the solvent used, aromatic hydrocarbons such as benzene and toluene, and ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane are preferable. The reaction temperature can be set to any temperature from 20 ° C to the reflux temperature of the reaction mixture, but it is preferably carried out at the reflux temperature.

Method F is a method suitable for the synthesis of the compound of the present invention in which Z ² is an imino group and through which Z ² is an oxygen atom. The starting material of the formula [XVIII] can be synthesized by a known method. The compound of formula [XVIII] and the formula [I
The compound of the formula [XIX] can be obtained by reacting V] or the compound of the formula [V] in the presence of a base in an inert solvent. The conditions of the base, solvent and reaction temperature used in the reaction are almost the same as those in Step 2 of Method A. Then, the compound of the formula [XIX] can be hydrolyzed under acidic conditions to obtain the compound of the present invention of the formula [VII]. The acid used is preferably a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, etc., and more preferably a diluted aqueous solution thereof. The reaction temperature can be set to any temperature from 20 ° C to the reflux temperature of the reaction mixture, but it is preferably carried out at the reflux temperature.

Method G is a method suitable for synthesizing the compound of the present invention in which A is a halogen atom or a cyano group. Formula [XX]
The compound of the formula [XXI] can be obtained by reacting the malonic acid derivative of the above with the (thio) ureas of the formula [XIII] in the presence of a base in an inert solvent. Examples of the base used include metal alkoxides such as sodium ethoxide, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as potassium carbonate, sodium hydride and the like. Examples of the solvent include lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, ethers such as 1,4-dioxane, dimethylformamide and the like. The reaction temperature can be set to any temperature from 0 ° C. to the reflux temperature of the reaction mixture.
When both L ² and L ³ are halogen atoms, the reaction is carried out in a solvent such as dioxane without adding a base at any temperature from 0 ° C. to the reflux temperature of the reaction mixture to give a compound of formula [XXI]
Can be obtained.

The compound of formula [XXII] can be obtained by reacting the compound of formula [XXI] with phosphorus oxyhalide, phosphorus trihalide or thionyl halide. In some cases, the presence of a base facilitates the process. Examples of phosphorus oxyhalides include phosphorus oxychloride and phosphorus oxybromide, examples of phosphorus trihalides include phosphorus trichloride and phosphorus tribromide, and examples of thionyl halides include thionyl chloride and thionyl bromide. As the base, organic bases such as pyridine and triethylamine are preferable.

The compound of formula [XXIII] can be obtained by reacting the compound of formula [XXII] with a metal cyanide compound in an inert solvent. It is preferable to use sodium cyanide or potassium cyanide copper cyanide as the metal cyanide compound. Examples of the solvent include lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane, and dimethylformamide. The reaction temperature can be set to any temperature from 0 ° C. to the reflux temperature of the reaction mixture.

Method H is a method suitable for the synthesis of A as an alkylthio group, an alkylsulfinyl group or an alkylsulfonyl group. The compound of formula [XXIV] can be obtained by reacting the compound of formula [XXII] with a metal salt of alkylmecaptan in an inert solvent. Examples of the metal of the metal salt of alkyl mercaptan include sodium and potassium. As the solvent, ethers such as 1,2-dimethoxyethane and tetrahydrofuran are preferable, but excess mercaptan may be used as the solvent. Reaction temperature is 0
Any temperature from ° C to the reflux temperature of the reaction mixture can be set.

A compound of formula [XXV] can be obtained by reacting a compound of formula [XXIV] with an equimolar amount of peroxide in an inert solvent. Furthermore, by reacting the compound of the formula [XXV] with an equimolar amount of peroxide, the compound of the formula [XXVI]
Can be obtained. Alternatively, by reacting the compound of the formula [XXIV] with twice the molar amount of the peroxide, the compound of the formula [XXV
The compound of formula [XXVI] can also be obtained without isolating the compound of []. Examples of the peroxide used include hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid and the like. As the solvent, alcohols such as methanol and ethanol, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, water and acetic acid are used.
The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but is preferably 0 ° C to 30 ° C.

Method I is a method of converting the hydrogen atom of the uracil derivative of the formula [XXVII] in which R ² is a hydrogen atom into a halogen atom, a nitro group or a thiocyanate group to obtain the compound of the present invention of the formula [XXVIII]. As the halogenating agent, it is preferable to use chlorine, sulfuryl chloride or N-chlorosuccinimide for chlorination, bromine, sulfuryl bromide or N-bromosuccinimide for bromination, and iodine or iodine monochloride for iodination. As the solvent, acetic acid or a halogenated hydrocarbon such as dichloromethane or carbon tetrachloride is preferably used. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but 20 ° C
It is preferable to carry out in the range from to the reflux temperature.

As the nitrating agent, nitric acid or a mixture of nitric acid and sulfuric acid is preferably used. As the solvent, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane or acetic acid is preferable, but the solvent may not be used. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but is preferably 0 ° C to 50 ° C. As the thiocyanating agent, it is preferable to generate thiocyanogen using ammonium thiocyanate and bromine. As the solvent, it is preferable to use halogenated hydrocarbons such as dichloromethane and carbon tetrachloride, ethers such as 1,2-dimethoxyethane and tetrahydrofuran, or acetic acid. The reaction temperature can be set to any temperature from 0 ° C to 50 ° C, but is preferably 0 ° C to 30 ° C.

Method J is the conversion of the methyl group of the uracil derivative of the formula [XXIX] in which R ² is a methyl group to a halomethyl group to obtain the compound of the present invention of the formula [XXX], and further the halomethyl of the compound of the formula [XXX]. Group is converted to an alkoxymethyl group, an alkylthiomethyl group or a hydroxymethyl group to obtain a formula [XXXI
I] or the compound of the formula [XXXIII].

In step 1, the compound of formula [XXIX] is converted to N
It is possible to react with -chloro- or N-bromosuccinimide to obtain 5-chloromethyl and 5-bromomethyl compounds of the formula [XXX]. The solvent is preferably a halogenated hydrocarbon such as carbon tetrachloride. The reaction temperature can be set at any temperature from 50 ° C. to the reflux temperature of the reaction mixture, but it is preferably carried out at the reflux temperature. In this reaction, it is advantageous to add a radical initiator such as benzoyl peroxide or azobisisobutyronitrile, or to carry out under ultraviolet irradiation.

In step 2, the 5-halomethyl compound of the formula [XXX] is reacted with the alkali metal alcoholate or thioalcoholate of the formula [XXXI] to give the 5-halomethyl compound of the formula [XXXII].
Alkoxymethyl and 5-alkylthiomethyl compounds can be obtained. The alkali metal alcoholate and thioalcolate of the formula [XXXI] used can be easily synthesized by reacting an alcohol or mercaptan with an alkali metal. As a solvent used, ethers such as 1,2-dimethoxyethane and tetrahydrofuran are preferable, but an excess alcohol or mercaptan may be used as a solvent. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture.
It is preferable to carry out at ° C.

In step 3, the 5-halomethyl compound of formula [XXX] is hydrolyzed in the presence of a base to give a 5-hydroxymethyl compound of formula [XXXIII]. The base used is preferably an alkali metal carbonate such as sodium carbonate or an alkali metal hydrogen carbonate such as sodium hydrogen carbonate. The reaction temperature can be set to any temperature from 0 ° C to the reflux temperature of the reaction mixture, but is preferably 0 ° C to 30 ° C.

Method K is a uracil compound having a hydrogen atom at the 3-position represented by the formula [XXXIV] and the compound of the formula [XXXV] in the presence of a base.
This is a method of obtaining a compound of formula [I] by reacting in an inert solvent. Examples of the compound of the formula [XXXV] include halogenated aromatic compounds having an electron-withdrawing substituent, and examples of halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the base include alkali metal alkoxides such as sodium ethoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, or sodium hydride. Examples of the solvent include lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethers such as 1,2-dimethoethane, dichloromethane, 1,2- Examples thereof include halogenated hydrocarbons such as dichloroethane, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, and mixed solvents thereof. Generally it is preferred to use sodium hydride as the base in a tetrahydrofuran, dimethylformamide or dimethylsulfoxide solvent. The reaction temperature can be set to any temperature from -30 ° C to the reflux temperature of the reaction mixture.

Further, in each production method (method A to method K), the molar ratio of each reaction substance is not particularly limited, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto. When the compound of the present invention needs to be purified, it can be separated and purified by an arbitrary purification method such as recrystallization and column chromatography. Among the compounds included in the present invention, the compounds having an asymmetric carbon atom include optically active compounds (+) and (−).

Further, when there are configurational isomers, cis isomers and trans isomers are included.

In using the compound of the present invention as a pest controlling agent, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth or the like, alcohols such as water, methanol, ethanol, benzene, toluene, Aromatic hydrocarbons such as xylene, chlorinated hydrocarbons, ethers, ketones, esters such as ethyl acetate, and acid amides such as dimethylformamide can be mixed and applied, if desired. By adding an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc., it can be put into practical use as an arbitrary formulation such as emulsion, oil, wettable powder, granule, flowable agent. .

If desired, it may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like during formulation or spraying. The application dose of the compound of the present invention varies depending on the application scene, application time, application method, target pests, cultivated crops, etc., but in general, about 0.005 to 50 kg per hectare of the active ingredient is suitable.

Next, the compounding ratios and types of various preparations of the present invention will be described below.

[0060]

[Table 1]   ──────────────────────────────────                                                     Other ingredients                   Active ingredient Carrier Surfactant (auxiliary agent)   ──────────────────────────────────     Emulsion 1 to 25 52 to 95 3 to 20 0 to 20     Oil 1-30 57-99     Flowable agent 1-70 10-90 1-200-10     Hydrating agent 1-70 15-93 3-10 0-5     Powder 0.01 to 30 67 to 99.5 0 to 3     Granules 0.01 to 30 67 to 99.5 0 to 8   ────────────────────────────────── Numerical values in the above table indicate% by weight.

Upon application, emulsions, oils, flowables and wettable powders are diluted with a predetermined amount of water and then sprayed, while powders and granules are directly sprayed without being diluted with water.

Next, examples of each component in each of the above-mentioned preparations will be given. Emulsion Active ingredient: Compound of the present invention Carrier: Xylene, dimethylformamide, methylnaphthalene, cyclohexanone, dichlorobenzene,
Isophorone surfactant: Sorpol 2680, Sorpol 3005X, Sorpol 3353 Other components: Piperonyl butoxide, benzotriazole oil Active ingredient: Compound of the present invention: Xylene, methylcellosolve, Kerosene flowable agent Active ingredient: Compound of the present invention Body: Water surfactant: Lunox 1000C, Solpol 3353, Soprofer FL, Nipol, Aglycol S-710, Sodium lignin sulfonate Other ingredients: Zansan gum, formalin, ethylene glycol, propylene glycol wettable powder Active ingredient: Compound of the present invention Carrier: Calcium carbonate, kaolinite, Sieglite D, Sieglite PFP, diatomaceous earth, talc Surfactant: Solpol 5039, Lunox 1000C, calcium lignin sulfonate, sodium dodecylbenzene sulfonate, Solpol 5050, Lepore 005D, Sorpol 5029-0 Other ingredient: Carplex 80 Dusts active ingredient: Present compound responsible body: calcium carbonate, kaolinite, Zeeklite D, talc Other ingredients: diisopropyl phosphate, Carplex 80 Granules (1) Active ingredient: Compound of the present invention carrier: Calcium carbonate, kaolinite, bentonite, talc Other components: Calcium lignin sulfonate, polyvinyl alcohol granules (2) [bait agent] Active ingredient: Compound of the present invention carrier: wheat flour, Bran, corn grit, siegrite D Other ingredients: paraffin, soybean oil

[0063]

EXAMPLES Examples (Synthesis Examples, Formulation Examples, Test Examples) Hereinafter, the present invention will be specifically described with reference to Examples (Synthesis Examples, Formulation Examples, Test Examples).

[Synthesis Example] The compounds included in the present invention are
Although prepared or could be prepared based on the synthetic examples shown below, the present invention is not limited to these compounds.

Synthesis Example 1 3- {4- (2-pyrimidyloxy) phenyl} -6-
(2-Chlorophenyl) -2,4 (1H, 3H) -pyrimidinedione (inventive compound No. 1.37) sodium hydride (purity 55
%) 0.30 g was added to dimethylformamide 20 mL, and the mixture was stirred at 0 ° C. with ethyl 3-amino-3- (2-chlorophenyl).
2-Propenoate (1.13 g) was added dropwise. After stirring at room temperature for 15 minutes, 1.30 g of ethyl (2-pyrimidyloxy) phenylcarbamate was added. After stirring at 110 ° C. for 3 hours, the solvent was distilled off under reduced pressure. The residue was dissolved in 100 mL of water, washed with diethyl ether, and then added to a mixed solution of 50 g of ice and 20 mL of concentrated hydrochloric acid. The precipitated crystals were collected by filtration and dried under reduced pressure to obtain 0.70 g of a crude product. The crystals were recrystallized from isopropyl alcohol to obtain 0.46 g of the desired compound.

Melting point: 260.5-263.0 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δ ppm): 5.68 (1 H, s),
6.75 ~ 6.95 (1H, m), 7.23 (4H, s), 7.39 (4H, s), 8.0
0 ~ 8.40 (2H, m), 11.6 (1H, bs).

Synthesis Example 2 3- (4-trifluoromethoxyphenyl) -5-bromo-6- (2-fluorophenyl) -2,4 (1H, 3
H) -pyrimidinedione (inventive compound No. 1.6) sodium hydride (purity 55
%) 2.4 g was added to 50 mL of dimethylformamide, and 25 mL of a dimethylformamide solution of 10.5 g of ethyl 3-amino-3- (2-fluorophenyl) -2-propenoate was added dropwise under stirring at 0 ° C. After stirring at room temperature for 15 minutes, the mixture was cooled to −30 ° C., and then 25 mL of a dimethylformamide solution containing 10.3 g of 4-trifluoromethoxyphenyl isocyanate was added dropwise. The mixture was gradually warmed to room temperature and then stirred at room temperature for another 3 hours. After the solvent was distilled off under reduced pressure, 200 mL of water was added and dissolved, and the mixture was washed twice with diethyl ether. Ice this water solution
It was added to a mixed solution of 100 g and concentrated hydrochloric acid (50 mL), and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 11.2 g of a crude product.
The crystals were washed with 100 mL of heated diisopropyl ether and then dried to give 3- (4-trifluoromethoxyphenyl) -6- (2-fluorophenyl)-.
10.1 g of 2,4 (1H, 3H) -pyrimidinedione was obtained.

3- (4-trifluoromethoxyphenyl) -6- (2-fluorophenyl) -2,4 (1H,
1.0 g of 3H) -pyrimidinedione was added to 20 mL of acetic acid, and 0.3 mL of bromine was added dropwise with stirring at room temperature. After stirring at room temperature for 1 hour, the mixture was added to 100 mL of ice water, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain a crude product. The crystals were washed with hot diisopropyl ether and dried to give 3- (4-trifluoromethoxyphenyl) -5-bromo-6- (2-fluorophenyl) -2,4 (1H,
1.2 g of 3H) -pyrimidinedione was obtained.

Melting point: 235.0-238.0 ° C ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δppm): 7.00 to 7.70 (4
H, m), 7.31 (4H, s), 12.10 (1H, bs).

Synthesis Example 3 3- (4-trifluoromethoxyphenyl) -5-cyano-6- (2-fluorophenyl) -2,4 (1H, 3
H) -pyrimidinedione (inventive compound No. 1.5) 3- (4-trifluoromethoxyphenyl) -5-bromo-6- (2-fluorophenyl) -2,4 (1H, 3H) -pyrimidinedione 0.70
g and 0.45 g of cuprous cyanide were added to 20 mL of N-methyl-2-pyrrolidone, and the mixture was stirred at 200 ° C. for 3 hours. The reaction solution was added to a cold aqueous solution of ammonium acetate, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain a crude product. This was purified by preparative thin layer chromatography using a mixed solvent of chloroform and ethyl acetate as a developing solvent to obtain 0.24 g of the desired compound.

Melting point: 259.0-265.5 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δppm): 7.05-7.75 (4H,
m), 7.31 (4H, s), 12.8 (1H, bs).

Synthesis Example 4 3- (4-trifluoromethoxyphenyl) -5-aminocarbonyl-6- (2-fluorophenyl) -2,4
(1H, 3H) -Pyrimidinedione (Compound of the present invention No. 1.39) 3- (4-trifluoromethoxyphenyl) -5-cyano-6- (2-fluorophenyl) -2,4 (1H, 3H) -pyrimidine Zion 0.5 g
Was added to 10 mL of concentrated sulfuric acid, and the mixture was stirred at 70 ° C for 3 hours. The reaction solution was added to 100 g of ice, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain a crude product. The crystals were washed with hot diisopropyl ether and dried to obtain 0.42 g of the desired compound.

Melting point:> 300 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6 + CD ₃ OD, TMS, δppm): 7.00
~ 7.70 (3H, m), 7.37 (4H, s).

Synthesis Example 5 3- (3,4-dichlorophenyl) -5-methyl-6-
(2,6-difluorophenyl) -2,4 (1H, 3
H) -pyrimidinedione (inventive compound No. 1.19) sodium hydride (purity 55
%) 0.30 g was added to dimethylformamide 10 mL, and a solution of ethyl 3-amino-3- (2,6-difluorophenyl) -2-methyl-2-propenoate 1.2 g in dimethylformamide 5 mL was added dropwise with stirring at 0 ° C. After stirring at room temperature for 30 minutes, the mixture was cooled again to 0 ° C, and then 1.0 g of 3,4-dichlorophenylisocyanate was added. After stirring at room temperature for 8 hours, the solvent was distilled off under reduced pressure. The residue was dissolved in 100 mL of water, washed with diethyl ether, and then added to a mixed solution of 50 g of ice and 20 mL of concentrated hydrochloric acid. It was extracted with 100 mL of ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate,
Then, the solvent was distilled off under reduced pressure to obtain a crude product. The crystals were washed with hot diisopropyl ether and dried to obtain 0.62 g of the desired compound.

Melting point: 205.5-208.0 ° C. ¹ H-NMR (CDCl ₃ , TMS, δppm): 1.80 (3H, s), 6.60 to 7.55
(6H, m), 10.24 (1H, bs).

Synthesis Example 6 3- (4-trifluoromethoxyphenyl) -6- (2
-Chlorophenyl)-(1H, 3H) -pyrimidine-2
-On-4-thione (Compound of the present invention No. 1.4) Sodium hydride (Purity 55
%) 2.0 g was added to 100 mL of dimethylformamide, and 7.9 g of ethyl 3-amino-3- (2-chlorophenyl) -2-propenoate was added dropwise with stirring at 0 ° C. After stirring for 15 minutes at room temperature, 8.7 g of ethyl 4-trifluoromethoxyphenyl carbamate was added. After stirring at 100 ° C. for 4 hours, the solvent was distilled off under reduced pressure. Dissolve the residue in 200 mL of water,
It was washed twice with diethyl ether. 100 g of this water solution
And 50 mL of concentrated hydrochloric acid were added to the mixture. The precipitated crystals were collected by filtration and dried under reduced pressure to obtain 10.7 g of a crude product. After washing the crystals with hot diisopropyl ether,
By drying, 3- (4-trifluoromethoxyphenyl) -6- (2-chlorophenyl) -2,4 (1
9.7 g of (H, 3H) -pyrimidinedione was obtained. 3- (4-
Trifluoromethoxyphenyl) -6- (2-chlorophenyl) -2,4 (1H, 3H) -pyrimidinedione 0.
5 g and Lawesson's Reagent (1.0 g) were added to 20 mL of hexamethylphosphoric triamide, and the mixture was stirred at 150 ° C. for 6 hours. This reaction solution was added to 100 mL of cold 5% hydrochloric acid water, and 100 mL of ethyl acetate was added for extraction. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a crude product. This was purified by preparative thin layer chromatography using a mixed solvent of chloroform and ethyl acetate as a developing solvent to obtain 0.26 g of the desired compound.

Melting point: 229.0-234.0 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δ ppm): 6.60 (1 H, s),
7.29 (4H, s), 7.42 (4H, s).

Synthesis Example 7 3- (4-trifluoromethoxyphenyl) -6-
(2,6-difluorophenyl)-(1H, 3H) -2
-Thion-4-one (Compound of the present invention No. 1.43) Sodium hydride (Purity 55
%) 0.4 g was added to dimethylformamide 20 mL, and a solution of ethyl 3-amino-2- (2,6-difluorophenyl) -2-propenoate 2.0 g in dimethylformamide 5 mL was added dropwise with stirring at 0 ° C. After stirring for 15 minutes at room temperature, -30 ℃
After cooling, 2.0 g of (4-trifluoromethoxyphenyl) isothiocyanate was added dropwise. After warming to room temperature, the mixture was further stirred at room temperature for 3 hours. After the solvent was distilled off under reduced pressure, it was poured into cold 5% hydrochloric acid water and extracted with ethyl acetate. The organic layer was washed with water and dried, and then the solvent was distilled off under reduced pressure to obtain a crude product. This was purified by preparative thin layer chromatography using chloroform as a developing solvent to obtain 0.08 g of the desired compound.

Melting point: 233.0-240.0 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δ ppm): 6.12 (1 H, s),
7.10 ~ 7.70 (3H, m), 7.38 (4H, s), 13.00 (1H, s).

Synthesis Example 8 3- (4-trifluoromethylphenyl) -6-phenyl-2,4 (1H, 3H) -pyrimidinedione (inventive compound No. 2.10) sodium hydride (purity 55
%) 0.6 g was added to dimethylformamide 30 mL, and a solution of ethyl 3-amino-3-phenyl-2-propenoate 2.5 g in dimethylformamide 5 mL was added dropwise with stirring at 0 ° C. After stirring for 15 minutes at room temperature, 3.0 g of ethyl 4-trifluoromethylphenyl carbamate was added. Then 120 ℃
After stirring for 3 hours, the solvent was distilled off under reduced pressure. 10 residues
Dissolve in 0 mL of water, wash with diethyl ether, then ice 50 g
And 20 mL of concentrated hydrochloric acid were added. The precipitated crystals were collected by filtration and dried under reduced pressure to give a crude product. The crystals were washed with hot diisopropyl ether and dried to obtain 2.2 g of the target compound.

Melting point:> 300 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δ ppm): 5.98 (1 H, s),
7.20 ~ 7.90 (9H, m), 11.65 (1H, bs).

Synthesis Example 9 3- (4-trifluoromethylphenyl) -5-iodo-6-phenyl-2,4 (1H, 3H) -pyrimidinedione (invention compound No. 2.12) 3- (4-tri Fluoromethylphenyl) -6-phenyl-2,4 (1H, 3H)-
0.7 g of pyrimidinedione was added to 20 mL of methylene chloride, and 1.0 mL of iodine monochloride was added dropwise with stirring at room temperature. After stirring at room temperature for another 1 hour, the mixture was added to ice water. Chloroform (50 mL) was added for extraction, the organic layer was washed with aqueous sodium thiosulfate solution and brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crystals were washed with hot diisopropyl ether to give the desired compound.
0.5g was obtained. Melting point: 297.0-299.0 ° C ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δppm): 7.40 to 8.00 (9
H, m), 11.95 (1H, bs).

Synthesis Example 10 3- (2,3,6-trifluorophenyl) -6-heptafluoropyropyr-2,4 (1H, 3H) -pyrimidinedione (invention compound No. 3.4) sodium hydride ( Purity 55
%) 0.22 g of dimethylformamide in 15 mL of solution was stirred at 0 ° C. under stirring with ethyl 3-amino-4,4,5,5,6,6,6,6.
A solution of 1.42 g of 6-heptafluoro-2-hexenoate in 3 mL of dimethylformamide was added dropwise. After stirring at room temperature for 30 minutes, a solution of ethyl (2,3,6-trifluorophenyl) carbamate (1.0 g) in dimethylformamide (3 mL) was added dropwise. After stirring at room temperature for 15 minutes, the mixture was further stirred at 120 ° C. for 3 hours. After the solvent was distilled off under reduced pressure, 100 mL of water was added to dissolve the residue, and the mixture was washed with diethyl ether and then added to a mixed solution of 50 g of ice and 20 mL of concentrated hydrochloric acid. After extraction with ethyl acetate, the organic layer was washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product. This was recrystallized from a mixed solvent of diisopropyl ether and isopropyl alcohol to obtain 0.32 g of the target compound.

Melting point: 157.5-160.0 ° C. ¹ H-NMR (CDCl ₃ + DMSO d-6, TMS, δ ppm): 6.19 (1 H, s),
7.00 ~ 7.40 (2H, m).

Synthesis Example 11 3- (2,6-dichloro-4-trifluoromethylphenyl) -6-methylsulfonyl-2,4 (1H, 3H)
-Pyrimidinedione (inventive compound No. 3.1) 3- (2,6-dichloro-4)
-Trifluoromethylphenyl) -6-bromo-2,4
0.81 g of (1H, 3H) -pyrimidinedione was added to 5 mL of dimethylformamide, and 0.35 g of methyl mercaptan soda was added with stirring at room temperature. After stirring at 80 ° C for 2 hours, the mixture was cooled to room temperature and added to chilled dilute hydrochloric acid. Ethyl acetate
100 mL was added for extraction, the organic layer was washed with diluted hydrochloric acid and water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. This was recrystallized using a mixed solvent of hexane and isopropyl ether to give 3- (2,
6-dichloro-4-trifluoromethylphenyl) -6
0.33 g of -methylthio-2,4 (1H, 3H) -pyrimidinedione was obtained.

3- (2,6-dichloro-4-trifluoromethylphenyl) -6-methylthio-2,4 (1H,
0.5 g of 3H) -pyrimidinedione was added to 5 mL of methylene chloride, and 5 mL of a methylene chloride solution of 0.57 g of m-chloroperbenzoic acid was added dropwise with stirring at 0 ° C. After stirring at room temperature for 2 hours, the mixture was added to ice water and extracted with methylene chloride. The organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This was washed with n-hexane and dried to obtain 0.17 g of the desired compound.

Melting point: 219.0-222.0 ° C. ¹ H-NMR (CDCl ₃ , TMS, δppm): 3.20 (3H, s), 6.42 (1H, s),
7.63 (2H, s).

The compounds shown in Tables 2 to 4 were synthesized or could be synthesized according to the above synthesis examples. Table 2 to 4
Q1 to Q61 are groups represented by the following formula.

[0089]

[Chemical 27]

[0090]

[Chemical 28]

[0091]

[Chemical 29]

[0092]

[Chemical 30]

Table 2

[0094]

[Chemical 31]

[0095]

[Table 2] ─────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ─────────────────────────────────── 1.1 HH 2-Cl 2 -F-4,5-Cl ₂ OO 220.0-222.0 1.2 HH 2-F 3,4-Cl ₂ OO 264.0-265.0 1.3 HH 2-Cl-6-F 3,4-Cl ₂ OO 255.0-257.0 1.4 HH 2 -Cl 4-OCF ₃ OS 229.0-234.0 1.5 H CN 2-F 4-OCF ₃ OO 259.0-265.5 1.6 H Br 2-F 4-OCF ₃ OO 235.0-238.0 1.7 HI 2-F 4-OCF ₃ OO 230.5- 233.0 1.8 H Cl 2,6-F ₂ 4-OCF ₃ OO 248.0-252.0 1.9 H Br 2,6-F ₂ 4-OCF ₃ OO 244.0-246.0 1.10 HI 2,6-F ₂ 4-OCF ₃ OO 233.5- 235.0 1.11 H CH ₃ 2-Cl 4-Cl OO 242.5-246.0 1.12 H CH ₃ 2-Cl 4-CF ₃ OO 233.0-236.0 1.13 H CH ₃ 2-Cl 4-OCHF ₂ OO 226.5-232.0 1.14 H CH ₃ 2 -Cl 2-F-4-Cl OO 218.5-225.0 1.15 H CH ₃ 2-Cl 3,4-Cl ₂ OO 209.0-211.5 1.16 H CH ₃ 2-F 4-OCF ₃ OO 215.0-218.0 1.17 H CH ₃ 2 -F 3,4-Cl ₂ OO 208.0-213.5 1.18 H CH ₃ 2,6-F ₂ 4-OCF ₃ OO 241.0-246.0 1.19 H CH ₃ 2,6-F ₂ 3,4-Cl ₂ OO 205. 5-208.0 1.20 H CH ₃ 2-Cl-6-F 4-OCF ₃ OO 238.5-240.0 1.21 H CH ₃ 2-Cl-6-F 3,4-Cl ₂ OO 219.0-222.5 1.22 H CH ₂ CH ₃ 2 -Cl 4-OCF ₃ OO 236.0-237.5 1.23 H CH ₂ CH ₃ 2-Cl 3,4-Cl ₂ OO 250.0-251.5 ────────────────────── ──────────────

[0096]

[Table 3] Table 2 (continued) ──────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ──────────────────────────────────── 1.24 H Cl 2,6-F ₂ 3,4-Cl ₂ OO 235.0-237.0 1.25 H Br 2,6-F ₂ 3,4-Cl ₂ OO 264.0-266.0 1.26 HI 2,6-F ₂ 3,4- Cl ₂ OO 280.0-281.0 1 27 CH ₂ OCH ₃ H 2,6-F ₂ 3,4-Cl ₂ OO 140.0-142.0 1.28 HH 2-Cl 3-Cl-4-OCHF ₂ OO 194.0-195.0 1.29 HH 2- Cl 3-Cl-4-OCF ₃ OO 227.0-230.0 1.30 HH 2-Cl 3-Cl-4-OCBrF ₂ OO 199.0-200.0 1.31 H Cl 2-Cl 3,4-Cl ₂ OO 236.0-238.0 1.32 H Br 2 -Cl 3,4-Cl ₂ OO 218.0-219.0 1.33 HI 2-Cl 3,4-Cl ₂ OO 217.0-219.0 1.34 H Br 2,4-Cl ₂ 4-CF ₃ OO 257.0-258.0 1.35 H Br 2,4 -Cl ₂ 4-OCF ₃ OO 248.0-249.0 1.36 HH 2-Cl 4-CF ₂ CF ₃ OO> 300.0 1.37 HH 2-Cl 4-O (Q43) OO 260.5-263.0 1.38 HH 2-Cl 3-Cl-4 -OCF ₂ CHF ₂ OO 226.0-227.0 1.39 H CONH ₂ 2-F 4-OCF ₃ OO> 300.0 1.40 HH 2-Cl 3-NO ₂ -4-CH ₃ OO 254.0-256.0 1.41 HH 2-Cl 3-NO ₂ -4-Cl OO 214.0-216.0 1.42 HH 2-Cl 4-OCF ₃ SO 255.0-258.0 1.43 HH 2,6-F ₂ 4-OCF ₃ SO 233.0-240.0 1.44 HH 2-Cl 3-Cl- 4-NO ₂ OO 238.0-240.0 1.45 HH 2,6-F ₂ 3-Cl-4-Br OO 237.0-238.0 ──────────────────────── ─────────────

[0097]

[Table 4] Table 2 (continued) ──────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ──────────────────────────────────── 1.46 HH 2,6-F ₂ 3,4-Cl ₂ OS 222.0-225.0 1.47 HH 2,6-F ₂ 4-OCF ₃ OS 1.48 HH 2,6-F ₂ 4-CF ₃ OS 1.49 HH 2,6- F ₂ 4-OCF ₃ SS 1.50 HH 2-Cl 3,4-Cl ₂ OS 1.51 HH 2-Cl 4-CF ₃ OS 1.52 HH 2-Cl 4-OCF ₃ SS 1.53 H CN 2-Cl 4-OCF ₃ OO 1.54 H CN 2-Cl 3,4-Cl ₂ OO 1.55 H CN 2,6-F ₂ 4-OCF ₃ OO 1.56 H CN 2,6-F ₂ 3,4-Cl ₂ OO 1.57 H CONH ₂ 2-Cl 4-OCF ₃ OO 1.58 H CONH ₂ 2-Cl 3,4-Cl ₂ OO 1.59 H CONH ₂ 2,6-F ₂ 4-OCF ₃ OO 1.60 H CONH ₂ 2,6-F ₂ 3,4-Cl ₂ OO 1.61 H CH (CH ₃ ) ₂ 2-Cl 4-OCF ₃ OO 1.62 HC (CH ₃ ) ₃ 2-Cl 4-OCF ₃ OO 1.63 H (CH ₂ ) ₃ CH ₃ 2-Cl 4-OCF ₃ OO 1.64 HH 2-Cl 4-O (Q43-5-Cl) OO 1.65 HH 2-Cl 3-Cl-4-O (Q43) OO 1.66 HH 2-Cl 3-Cl-4-O (Q38-5-CF ₃ ) OO 1.67 HH 2-Cl 3-Cl-4-O (Q38-5-I) OO ──────────── ──────────────────────

[0098]

[Table 5] Table 2 (continued) ──────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ──────────────────────────────────── 1.68 HH 2-Cl 3-Cl-4-O (Q38-5-Cl) OO 1.69 HH 2-Cl 4-O (Q38-5-Br) OO 1.70 HH 2-Cl 4-O (Q38-5-CF ₃ -6-Cl) OO 1.71 HH 2-Cl 3-Cl-4-O (Q43-5-I) OO 1.72 HH 2-Cl 3-Cl-4-O (Q43-5-Cl) OO 1.73 HH 2 -Cl 4-O (Q43-5-I) OO 1.74 HH 2-Cl 3-NO ₂ -4-O (Q43-5-Cl) OO 1.75 HH 2-NO ₂ 3-NO ₂ -4-O (Q43 -5-Cl) OO 1.76 HH 2-NO ₂ 3-NO ₂ -4-O (Q43-5-CF ₃ ) OO 1.77 HH 2-NO ₂ 3-NO ₂ -4-O (Q41-6-Br) OO 1.78 HH 2-NO ₂ 4-O (Q43) OO 1.79 HH 2-NO ₂ 3-Cl-4-O (Q38) OO 1.80 HH 2-NO ₂ 3-CF ₃ -4-O (Q43-5- I) OO 1.81 HH 2-NO ₂ 3-Cl-4-O (Q38-5-CF ₃ ) OO 1.82 HH 2-Br 3-Cl-4-O (Q43-5-I) OO 1.83 HH 2-Br 4-O (Q43-5-CF ₃ -6-Cl) OO 1.84 HH 2-CF ₃ 3-Cl-4-O (Q38-5-CF ₃ ) OO 1.85 HH 2-CF ₃ 4-O (Q43- 5-CF ₃ -6-Cl) OO 1.86 HH 2,6-Cl ₂ 3-O (Q50) OO 1.87 HH 2,6-Cl ₂ 4-O (Q50) O O 1.88 HH 2,6-Cl ₂ 3-S (Q50) OO 1.89 HH 2,6-Cl ₂ 4-S (Q50) OO ──────────────────── ────────────────

[0099]

[Table 6] Table 2 (continued) ──────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ──────────────────────────────────── 1.90 HH 2,6-Cl ₂ 4-O (Q50-6-Cl) OO 1.91 HH 2,6-Cl ₂ 3-Cl-4-O (Q43-5-I) OO 1.92 HH 2,6- (OCH ₃ ) ₂ 3-O (Q50) OO 1.93 HH 2,6- (OCH ₃ ) ₂ 4-O (Q50) OO 1.94 HH 2,6- (OCH ₃ ) ₂ 4-O (Q50-6-Cl) OO 1.95 HH 2,6- (OCH ₃ ) ₂ 3-Cl-4-O (Q43-5-I) OO 1.96 HH 2,6-F ₂ 3-Cl-4-O (Q50) OO 1.97 HH 2-Cl 3-Cl-4-S (Q50) OO 1.98 HH 2-NO ₂ 4-O (Q50) OO 1.99 HH 2-Cl-6-F 4-O (Q50) OO ─────────── ────────────────────────

Table 3

[0101]

[Chemical 32]

[0102]

[Table 7] ─────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ─────────────────────────────────── 2.1 H CH ₃ H 3 , 4-Cl ₂ OO 253.0-255.0 2.2 H CH ₂ CH ₃ H 3,4-Cl ₂ OO 216.0-218.0 2.3 HHH 4-Cl OO 299.0-300.0 2.4 H Br H 4-Cl OO 266.0-267.0 2.5 HIH 4- Cl OO 282.0-284.0 2.6 HHH 4-OCHF ₂ OO 281.0-283.0 2.7 H Br H 4-OCHF ₂ OO 248.0-249.0 2.8 HIH 4-OCHF ₂ OO 214.0-216.0 2.9 HIH 3,5-Cl ₂ -4-0CF ₂ CHF ₂ OO> 300.0 2.10 HHH 4-CF ₃ OO> 300.0 2.11 H Br H 4-CF ₃ OO 294.0-295.0 2.12 HIH 4-CF ₃ OO 297.0-299.0 2.13 HH 3-Cl 3,4-Cl ₂ OO 274.0- 275.0 2.14 H Br 3-Cl 3,4-Cl ₂ OO 294.0-295.0 2.15 HI 3-Cl 3,4-Cl ₂ OO 277.0-279.0 2.16 HH 4-Cl 3,4-Cl ₂ OO> 300.0 2.17 H Br 4 -Cl 3,4-Cl ₂ OO> 300.0 2.18 HI 4-Cl 3,4-Cl ₂ OO> 300.0 2.19 H Br 3,4-Cl ₂ 4-CF ₃ OO> 300.0 2.20 HHH 2-F-4-O (C ₆ H ₃ -2-Cl-4-CF ₃ ) OO 238.0-239.0 2.21 H Br H 2-F-4-O (C ₆ H ₃ -2-C l-4-CF ₃ ) OO 237.0-239.0 2.22 HIH 2-F-4-O (C ₆ H ₃ -2-Cl-4-CF ₃ ) OO 237.0-238.0 2.23 HH 4-C ₆ H ₅ 4-OCF ₃ OO> 300.0 ───────────────────────────────────

[0103]

[Table 8] Table 3 (continued) ──────────────────────────────────── No. R ¹ R ² X _l Y ¹ _m Z ¹ Z ² Melting point (℃) ──────────────────────────────────── 2.24 HI 4-C ₆ H ₅ 4-OCF ₃ OO> 300.0 2.25 HH 4-Br 4-OCF ₃ OO> 300.0 2.26 HI 4-Br 4-OCF ₃ OO 224.0-225.0 2.27 H Br 3,4-Cl ₂ 4 -OCF ₃ OO> 300.0 2.28 HI 3,4-Cl ₂ 4-OCF ₃ OO 288.0-290.0 2.29 H Br 4-CF ₃ 4-OCF ₃ OO 221.0-222.0 2.30 HI 4-CF ₃ 4-OCF ₃ OO 231.0- 232.0 2.31 HHH 4-O (Q43) OO 2.32 H Cl H 4-O (Q43) OO 2.33 H Br H 4-O (Q43) OO 2.34 HIH 4-O (Q43) OO 2.35 H CN H 4-O (Q43 ) OO 2.36 H NO ₂ H 4-O (Q43) OO 2.37 HHH 4-O (Q43) OO 2.38 HHH 3-Cl-4-O (Q38-5-CF ₃ ) OO 2.39 HHH 3-Cl-4-O (Q38-5-Cl) OO 2.40 HHH 3-Cl-4-O (Q43-5-CF ₃ ) OO 2.41 HHH 3-O (Q50) OO 2.42 HHH 4-O (Q50) OO 2.43 HHH 3-Cl- 4-O (Q50-5-Cl) OO ────────────────────────────────────

[0104]

[Chemical 33]

[0105]

[Table 9] Table 4 ─────────────────────────────────── No. R ¹ R ² AY ² _r Z ¹ Z ² Melting point (℃) ─────────────────────────────────── 3.1 HH SO ₂ CH ₃ 2,6-Cl ₂ -4-CF ₃ OO 219.0-220.0 3.2 HH CF ₃ 2,6-Cl ₂ -4-CF ₃ OO> 300.0 3.3 HH CF ₂ Cl 2,6-Cl ₂ -4-CF ₃ OO> 300.0 3.4 HH CF ₂ CF ₂ CF ₃ 2,3,6-F ₃ OO 157.5-160.0 ──────────────────────────── ────────

[Formulation Examples] Next, formulation examples of the pest control agent containing the compound of the present invention as an active ingredient are shown, but the present invention is not limited thereto. In the following formulation examples,
“Parts” means parts by weight.

Formulation Example 1 Emulsion Compound of the present invention 5 parts xylene ───── 70 parts N, N-Dimethylformamide ───── 20 parts Solpol 2680 ───── 5 parts (non- Mixture of ionic and anionic surfactants: trade name of Toho Kagaku Kogyo Co., Ltd. The above is uniformly mixed to prepare an emulsion.

In use, the above emulsion was diluted 50 to 20000 times to obtain an amount of active ingredient of 0.005 to 50 kg per hectare.
Sprinkle so that

Formulation Example 2 Wettable powder Compound of the present invention ───── 25 parts Zyklite PFP ───── 66 parts (mixture of kaolinite and sericite: product name of Zyklite Industry Co., Ltd.) Solpol 5039 ─ ──── 4 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Carplex # 80 ────── 3 parts (White carbon: Shionogi Seiyaku Co., Ltd. trade name) Calcium lignin sulfonate ──── Mix and pulverize 2 parts or more to make wettable powder.

When using, the above-mentioned wettable powder should be used in an amount of 50 to 20000.
Diluted twice and the amount of active ingredient is 0.005 to 50 per hectare
Spread so that it becomes kg.

Formulation Example 3 Oil agent Compound of the present invention: 10 parts methyl cellosolve: 90 parts: 90 parts or more are uniformly mixed to obtain an oil agent. At the time of use, the above oil agent is sprinkled so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 4 Powder Compound of the present invention ───── 3.0 parts Carplex # 80 ────── 0.5 part (White carbon: Shionogi Pharmaceutical Co., Ltd. trade name) Clay ───── 95 parts Diisopropyl phosphate ───── 1.5 parts or more are uniformly mixed and pulverized to give a powder.

At the time of use, the above dust is sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 5 granules Compound of the present invention ───── 5 parts Bentonite ───── 54 parts Talc ───── 40 parts Calcium lignin sulfonate ─── 1 part The above is uniformly mixed and ground. Then, a small amount of water is added, and the mixture is stirred and mixed, granulated by an extrusion type granulator, and dried to obtain a granule.

At the time of use, the above granules are sprinkled so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 6 Flowable agent Compound of the present invention 35 parts Solpol 3353 10 parts (Nonionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000C ──── ─ 0.5 parts (anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) 1% Zansan gum aqueous solution ───── 20 parts (natural polymer) water ──── 34.5 parts Active ingredient (compound of the present invention) Except for the above components, the components are uniformly dissolved, the compound of the present invention is added, the mixture is stirred well, and wet milled in a sand mill to obtain a flowable agent.

When using the above flowable agent,
Diluted 20000 times and the amount of active ingredient is 0.00 per hectare
Sprinkle so that it is 5 to 50 kg.

[Test Example] Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples.

Test Example 1 Insecticidal test against brown planthopper 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was used as a test) was diluted with water containing a spreading agent to give 1000 The drug solution was prepared to have a ppm concentration. 1/2 this chemical
A sufficient amount was applied to the foliage of rice planted in a pot of 0,000 are. After air-drying, a cylinder was set up, 10 second-instar larvae of the brown planthopper were released per pot, capped, and stored in a temperature-controlled room. The survey was conducted after 6 days, and the mortality rate was calculated from the following formula. The test was conducted in a two-division system.

Mortality of mortality (%) = (number of mortality / number of larvae) × 100 As a result, the following compounds showed a mortality of 100%. Compounds of the present invention: 1.5, 1.7, 1.36, 2.12, 2.21, 2.24,
3.2, 3.3, 3.4.

Test Example 2 Insecticidal test against pearl oyster ladybird 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent. Then, adjust to a chemical solution of 1000ppm concentration, soak the tomato leaves in this solution for about 10 seconds, air-dry and place in a petri dish.
The head was released and the lid was put on it and stored in a thermostatic chamber at 25 ° C, and the mortality rate after 6 days was calculated from the following formula. The test was conducted in a two-division system.

Mortality of mortality (%) = (number of mortality / number of larvae) × 100 As a result, the following compounds showed a mortality of 100%. Compounds of the present invention: 1.3, 1.8, 1.11, 1.12, 1.13, 1.14,
1.15, 1.17, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.
25, 1.26, 1.28, 1.30, 1.31, 1.32, 1.33, 1.34, 1.3
6, 1.38, 2.2, 2.7, 2.8, 2.12, 2.21, 2.26, 2.2
7, 2.29, 2.30, 3.2, 3.3, 3.4.

Test Example 3 Insecticidal test against Spodoptera litura A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent to give 1000 ppm. Prepare a chemical solution of the concentration, immerse kanlan leaves in this chemical solution for about 10 seconds, air dry and put it in a petri dish, and release 10 second-infested larvae of diamondback moth in 10 petri dishes and cover with a hole. It was stored in a constant temperature chamber at 25 ° C., and the mortality rate after 6 days was calculated from the following formula. The test was conducted in a two-division system.

Mortality of mortality (%) = (number of mortality / number of mortality) × 100 As a result, the following compounds showed a mortality of 100%. The compound of the present invention: 1.2, 1.3, 1.4, 1.6, 1.7, 1.8,
1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.
19, 1.20, 1.21, 1.22, 1.27, 1.28, 1.29, 1.30, 1.3
1, 1.32, 1.33, 1.36, 1.38, 2.3, 2.4, 2.5, 2.7
, 2.11, 2.12, 2.18, 2.20, 2.21, 2.22, 2.26.

Test Example 4 Acaricidal efficacy test against scabbard mites The leaf of kidney bean was cut into a circle with a diameter of 3.0 cm using a leaf punch and placed on a wet filter paper on a styrene cup having a diameter of 7 cm. Ten head mite larvae were inoculated into each leaf. A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent to prepare a 1000 ppm concentration solution, and this solution was 2 mL per styrene cup was sprayed using a rotary spraying tower, stored in a thermostatic chamber at 25 ° C., and the mortality rate after 96 hours was calculated from the following formula. The test was conducted in a two-division system.

Mortality of mortality (%) = (number of mortality / number of larvae) × 100 As a result, the following compounds showed a mortality of 100%. Compounds of the present invention: 1.2, 1.3, 1.15, 1.24, 1.25, 1.26,
1.27, 1.31, 1.32, 1.33, 2.1, 2.11, 2.12, 2.16, 2.
17, 2.18, 2.21, 2.26, 3.1, 3.4.

Comparative Test Example 3,6-Diphenyluracil which is a known compound in the literature (in the general formula I, A = phenyl, B = phenyl, R ¹ = hydrogen atom, R ² = hydrogen atom, Z ¹ = oxygen atom, Z ² = Oxygen atom) is any pest at 1000 ppm concentration in Test Examples 1 to 4 above.
It did not show any activity against the brown planthopper, the pearl locust, the white-spotted mite, and the spider mite (mortality rate 0%).

[0128]

INDUSTRIAL APPLICABILITY The compound of the present invention has excellent insecticidal and acaricidal activity against many agricultural pests and mites, and has almost no adverse effect on mammals, fish and beneficial insects. Therefore, the compound of the present invention can provide a useful pest control agent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location A01N 43/60 101 8930-4H 43/76 8930-4H 43/78 B 8930-4H 43/80 102 8930-4H 43/82 8930-4H C07D 239/47 Z 7038-4C 239/48 7038-4C 239/553 239/54 239/56 7038-4C 239/58 7038-4C 239/60 7038-4C 401/04 8829-4C 401/12 8829-4C 401/14 8829-4C 403/04 8829-4C 403/12 8829-4C 403/14 8829-4C 405/04 8829-4C 405/12 8829-4C 405/14 8829- 4C 413/04 8829-4C 413/12 8829-4C 413/14 8829-4C 417/04 9051-4C 417/12 9051-4C 417/14 9051-4C C07F 7/10 A 8018-4H 7038-4C C07D 239 / 55 (72) Inventor, Kazuhiko Aimoto, 722, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Co., Ltd. Central Research Laboratory (72) Inventor Toshiyuki Hara 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama, Institute of Biological Sciences, Nissan Chemical Industries Ltd. (72) Inventor Masatake Kudo 1470, Shiraoka, Shiraoka-cho, Minami-Saitama, Saitama Prefecture, Institute of Biological Sciences, Nissan Chemical Industries (72) Inventor Yoichi Inoue 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture Nissan Chemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A general formula [I]: << In the formula, R ¹ is a hydrogen atom, a C _{1 to} C ₄ alkyl group, a C _{2 to} C ₄ alkenyl group, a C _{2 to} C ₄ alkynyl group, a C _{1 to} C ₄ haloalkyl group, and a C _{2 to} C ₄ alkoxyalkyl group. , Formyl group, C ₂ -C ₆
Alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl group, C ₃ -C ₆ alkoxycarbonylalkyl group, C ₂ -C ₆ cyanoalkyl group, a benzyl group, a phenyl group, an alkali metal or alkaline earth metal, R ² It is a hydrogen atom, a halogen atom, C ₁ -C ₄ alkyl group, C ₁ ~
C ₄ haloalkyl group, C ₁ -C ₄ hydroxyalkyl group, C ₂ ~
C ₄ alkoxyalkyl group, C ₂ -C ₄ alkylthioalkyl group, a thiol group, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ alkylsulfinyl group, C ₁ -C ₄ alkylsulfonyl group, C ₁ ~
C ₄ haloalkylthio group, C ₁ -C ₄ haloalkylsulfinyl group, C ₁ -C ₄ haloalkylsulfonyl group, hydroxy group, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy group, a formyl group, a cyano group, A nitro group, an amido group or a thiocyanate group, Z ¹ and Z ² each independently represent an oxygen atom, a sulfur atom or an imino group, and A is {However, X is a halogen atom, C ₁ -C ₄ alkyl group, C _1-
C ₄ alkoxy, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ haloalkoxy groups, C ₁ -C ₄ haloalkylthio group, an amino group, a cyano group or a nitro group, , 1 represents an integer of 0 to 5 (in the case of 2 to 5, X may be the same or different). }, An unsubstituted or optionally substituted naphthyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, Pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group (however, the optionally substituted substituents are a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkylthio group). Base, C ₁
To C ₄ haloalkyl group, C _{1 to} C ₄ haloalkoxy group, C _{1 to} C ₄
A haloalkylthio group, an amino group, a cyano group or a nitro group, and when the number of substituents is 2 or more, the substituents may be the same or different), C containing at least one fluorine atom ₁ -C ₆ haloalkyl group, a halogen atom, a cyano group, a nitro group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylthio group , A C _{1 to} C ₆ haloalkylsulfinyl group, a C _{1 to} C ₆ haloalkylsulfonyl group, a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ haloalkoxy group or a C _{2 to} C ₆ alkoxycarbonyl group, and A is Chemical 3] (However, X and l have the same meanings as described above.), An unsubstituted or optionally substituted naphthyl group, a furyl group, a thienyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group. Group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, pyridyl group, pyridazyl group, pyrimidyl group or pyrazyl group, B is [However, Y ¹ is a halogen atom, C _{1 to} C ₆ alkyl group, C ₂ to
C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₆ haloalkyl group, C ₂ -C ₆ haloalkenyl group, C ₂ -C ₆ haloalkynyl group, C ₃ -C ₆ halocycloalkyl group, C ₂ -C ₆ cyanoalkyl group, C ₁ -C ₆ hydroxyalkyl group, C ₂ -C ₆ carboxyalkyl group, C ₁ -C ₆ alkoxy group, C ₂ -C ₆ alkenyloxy group, C ₂ -C ₆ alkynyloxy group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₆ haloalkoxy group, C ₂ -C ₆ haloalkenyloxy group, C ₂ -C ₆
Haloalkynyloxy group, C ₃ -C ₆ halocycloalkyl alkoxy group, C ₄ -C ₇ halocycloalkyl alkoxy group, C ₁ -C ₆ alkylthio group, C ₂ -C ₆ alkenylthio group, C ₂ -C ₆ alkynylthio group, C ₃ -C ₆ cycloalkylthio group, C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₂ ~
C ₆ alkenylsulfinyl group, C ₂ -C ₆ alkynylsulfinyl group, C ₃ -C ₆ cycloalkyl alkylsulfinyl group, C ₁ ~
C ₆ haloalkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₂ -C ₆ alkenylsulfonyl group, C ₂ -C ₆ alkynylsulfonyl group, C ₃ -C ₆ cycloalkylsulfonyl group, C ₁ -C ₆ haloalkylsulfonyl group, C ₂ -C ₆ alkoxyalkyl group, C ₂ -C ₆ alkoxyalkoxy, C ₂ -C ₆
Haloalkoxyalkyl group, C ₂ -C ₆ haloalkoxy alkoxy group, C ₂ -C ₆ alkylthioalkyl group, C ₂ -C ₆ alkylthioalkoxy group, C ₃ -C ₆ alkoxycarbonylalkyl group, C ₃ -C ₆ alkylcarbonyl alkyl group, C ₂ ~
C ₆ alkoxycarbonyl group, C ₂ -C ₆ alkylcarbonyloxy group, C ₂ -C ₆ alkylcarbonyl group, C ₃ -C ₆
Alkenylcarbonyl group, C ₃ -C ₆ alkynyl group, C ₄ -C ₇ cycloalkylcarbonyl group, C ₂ -C ₆ haloalkylcarbonyl group, C ₂ -C ₆ alkoxycarbonyl group,
C ₂ -C ₆ haloalkoxycarbonyl groups, C ₃ -C ₆ alkoxycarbonylalkoxy group, nitro group, cyano group, hydroxy group, carboxyl group, thiocyanate group, isothiocyanate group, C ₂ -C ₆ thiocyanate alkyl group, C ₁ ~
C ₆ alkylsulfonyloxy group, C ₂ -C ₆ alkylthiocarbonyl group, an amino group (-NR ³ R ^4), aminocarbonyl group (-
CONR ³ R ⁴ ), aminocarbonyloxy group (-OCONR ³ R ⁴ ), amide group (-NR ³ COR ⁴ ), alkoxycarbonylamino group (-NR
³ CO ₂ R ⁴ ), aminosulfonyl group (-SO ₂ NR ³ R ⁴ ), thioamide group (-NR ³ CSR ⁴ ), methylenedioxy group, halomethylenedioxy group, ethylenedioxy group, haloethylenedioxy Group, trimethylsilyl group or {However, W is Or [Chemical 7] (However, R ³ and R ⁴ are each independently a hydrogen atom, C _{1 to} C ₆
Alkyl group, C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, C ₁ -C ₆ haloalkyl group, C ₂ -C ₆ haloalkenyl group,
C ₂ -C ₆ haloalkynyl group, C ₂ -C ₆ alkylcarbonyl group, C ₂ -C ₆ alkoxycarbonyl group, a phenyl group or a benzyl group, R ⁵ and R ⁶ are each independently hydrogen atom, a halogen atom , A C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group, a cyano group or a phenyl group, and q represents an integer of 0-2. ), N is an integer of 0 or 1, Ar is an unsubstituted or optionally substituted phenyl group, naphthyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thiazolyl group, isothiazolyl group. Group, oxazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, quinolyl group or quinoxalyl group (however, a substituent which may be substituted is a halogen atom, cyano group, nitro group, C ₁ -C ₄ alkyl group, C ₁ -C ₄ haloalkyl groups, C ₁ ~
C ₄ alkoxy, C ₁ -C ₄ Haroarukikoshi group, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ haloalkylthio group, C ₁ -C ₄ alkylsulfonyl group, C ₁ -C ₄ haloalkylsulfonyl groups, C ₂
~ C ₄ alkoxycarbonyl group, carboxyl group, amino group, mono C ₁ -C ₄ alkylamino group, di C ₁ -C ₄ alkylamino group, phenyl group, benzyl group, methylenedioxy group or halomethylenedioxy group In the case where there are two or more substituents, the substituents may be the same or different. }, M is an integer of 0 to 5 (provided that Y ¹ may be the same or different in the case of 2 to 5). ], An unsubstituted or optionally substituted naphthyl group, furyl group, thienyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, thiadiazolyl group, oxadiazolyl group, triazolyl group, Pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, quinolyl group, quinoxalyl group,
Benzofuryl group, benzothienyl group, indolyl group, benzoxazolyl group or benzothiazolyl group (however, as an optionally substituted substituent, a halogen atom, a cyano group, a nitro group, a C _{1 to} C ₄ alkyl group, C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ alkoxy groups, C ₁ -C ₄ haloalkoxy groups, C ₁ -C ₄ alkylthio groups, C ₁ -C ₄ haloalkylthio groups, C ₁ -C ₄ alkylsulfonyl groups, C ₁ -C ₄ haloalkylsulfonyl groups, C ₂ -C ₄ alkoxycarbonyl group, a carboxyl group, an amino group, mono C ₁ -C ₄ alkylamino group,
Di C ₁ -C ₄ alkylamino group, phenyl group, phenoxy group or benzyl group, and when two or more substituents, the substituents may be the same or different, and A is fluorine A C _{1 to} C ₆ haloalkyl group containing one or more atoms, a halogen atom, a cyano group, a nitro group, a C _{1 to} C ₆ alkylthio group, a C _{1 to} C ₆ alkylsulfinyl group, a C _{1 to} C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆
In the case of a haloalkylsulfinyl group, a C _{1 to} C ₆ haloalkylsulfonyl group, a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ haloalkoxy group or a C _{2 to} C ₆ alkoxycarbonyl group, B is {However, Y ² is a halogen atom, C _{1 to} C ₄ alkyl group, C ₁ to
C ₄ alkoxy, C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ haloalkoxy groups, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ haloalkylthio group, C ₁ -C ₄ alkylsulfinyl group, C ₁ To C ₄ haloalkylsulfinyl group, C _{1 to} C ₄ alkylsulfonyl group, C _{1 to} C ₄ haloalkylsulfonyl group, sulfonamide group, C _{2 to} C ₄ alkenyl group, C _{2 to} C ₄ haloalkenyl group, amino group, mono C ₁ -C ₄ alkylamino group, di C ₁ -C ₄ alkylamino group, C ₂ -C ₆ alkoxyalkoxy, C ₂ -C ₆ alkoxycarbonyl group, a cyano group or a nitro group, r is 3-5 (Provided that Y ^{2 s} are the same or different, and in the case of r = 3 and a tri-substituted product at the 2, 4, 5-position, the substituent Y ^{2 at the} 5-position is C ₁ -C ₄ alkoxy groups, C ₁ -C ₄ haloalkoxy groups, C ₂ -C ₆ alkoxyalkoxy, C ₂ -C ₆ alkoxy Indicates indicates not be a carbonyl group)}, and A is a phenyl group or a 3-bromo-4-methoxyphenyl group, uracil derivative B is represented by except when a phenyl group. " 2. In the general formula [I], A is (However, X and l have the same meanings as described above.), And B is (Wherein Y ¹ and m have the same meanings as described above), and A is a phenyl group or a 3-bromo-4-methoxyphenyl group, and B is a phenyl group, except. Compound of. 3. In the general formula [I], A is a C _{1 to} C ₆ haloalkyl group in which at least one fluorine atom is contained, a halogen atom, a cyano group, a nitro group, a C _{1 to} C ₆ alkylthio group, C ₁ to
C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ -C ₆ haloalkylsulfonyl group, C ₁ ~
C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group or a C ₂ -C ₆
Represents an alkoxycarbonyl group, and B is (Wherein Y ² and r have the same meanings as described above). 4. A pest control agent containing one or more uracil derivatives according to claim 1 as active ingredients. 5. A pest control agent containing one or more uracil derivatives according to claim 2 as active ingredients. 6. A pest control agent containing one or more uracil derivatives according to claim 3 as an active ingredient.