JPH0678308B2 - Phthalimide derivative and agricultural / horticultural germicide containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel phthalimide derivatives and agricultural and horticultural fungicides containing them as active ingredients.

2. Description of the Related Art Compounds similar to the phthalimide derivative of the present invention and known as agricultural fungicides are disclosed in JP-A-50-25736, JP-A-51-54924 and JP-A-52-125625. And the compounds are represented by the formula:

In the above formula, in the compound described in JP-A No. 50-25736, Ra and Rb each represent an ethyl group or an isopropyl group, and Rc and Rd are both hydrogen atoms. The compound described in JP-A-51-54924, Ra and Rb each represents an ethyl group or an isopropyl group, Rc and
One of Rd represents a hydrogen atom and the other represents a chlorine atom or a methyl group. The compounds described in JP-A-52-125625,
Ra and Rb each represent an ethyl group or an isopropyl group, and one of Rc and Rd represents a hydrogen atom and the other represents a methoxy group.

As a result of various searches for phthalimide compounds, the present inventors have found that a group of novel phthalimide derivatives exhibit bactericidal activity comparable to that of the above-described known similar compounds, and in particular, an important disease of cruciferous crops known as root-knot disease. The present invention has been completed by finding that it has an activity exceeding Plasmodiophola brassicae, which is the causative bacterium of the above, against known compounds.

Means for Solving the Problems That is, the present invention provides a novel phthalimide derivative having the following general formula (I) and an agricultural / horticultural fungicide containing the same.

(In the formula, R ¹ and R ² are the same or different from each other and represent a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group, respectively, and R ³ is a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group. represents a group, R ⁴ is a nitro group, an amino group, one or two aliphatic carboxylic acyl substituents amino group having a heterocyclic group, an aliphatic carboxylic acyl group, C ₂ -C ₄ alkenyl group , Or a C ₁ -C ₄ -substituted alkyl or C ₂ -C ₄ -substituted alkenyl group, which has 1 or 2 substituents and is selected from the following group: Group —XR ⁵ (X is oxygen atom,
A sulfur atom or -NH-, R ⁵ is a hydrogen atom, C ₃ -C ₈ cycloalkyl groups, C ₂ -C ₄ alkenyl groups, C ₂ -C ₄ alkynyl group, an aryl group, a carboxy group, an acyl groups, C ₁ - ₆ alkyl group or at least one cyano, nitro, C ₁
-C ₄ alkoxy, aryl, aryloxy or C ₁ -
C ₁ -C ₆ alkyl group having a C ₄ alkylamino substituent),
Halogen atom, heterocyclic group, carboxy group, thiocarboxy group, cyano group, aliphatic carboxylic acid acyl group, aromatic carboxylic acid acyl group, nitro group, di (C ₁ -C ₃ alkoxy)
Phosphoryl group and hydroxyimino group], and when R ⁴ is a group containing a carboxy group, a thiocarboxy group, or a carboxy or thiocarbonoxy group, their corresponding halides, esters, amides and salts thereof, or R ⁴ When is a group containing a hydroxyl group or a mercapto group, an ester thereof, or an acid addition salt thereof, when R ⁴ is a substituted or unsubstituted amino group.

When the compound of formula (I) is an ester or salt, the acid or alcohol used to form the ester and the acid or base that forms the salt can be selected from a wide variety of compounds, and the ester or salt formed can be used in agriculture and horticulture. There is no particular limitation as long as it is acceptable.

When R ⁴ represents a carboxy group, a thiocarboxy group, or an alkyl group or an alkenyl group containing 1 or 2 carboxy or thiocarboxy, and
When R ⁵ represents a carboxy group, the compounds of formula (I) can form salts. Examples of salts include, for example, alkali metals, alkaline earth metals and other metals, ammonium,
Examples thereof include salts of quaternary ammonium and organic amines. Examples of suitable salts include, for example, alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, trivalent metal salts such as aluminum and iron, ammonium salts, and tetrabutylammonium tetrahydrate. Quaternary ammonium salts represented by (C ₁ -C ₆ alkyl) ammonium salt, di- or tri- (C ₁ -C ₆ alkyl) amine, especially di- or tri- (C ₁ -C ₄ alkyl) amine Alternatively, cyclic amine salts such as organic amine salts represented by diethylamine, dipropylamine, trimethylamine, triethylamine, tripropylamine, pyridine salts and the like can be mentioned.

When R ⁴ represents a carboxy group, a thiocarboxy group, or an alkyl group or an alkenyl group containing 1 or 2 carboxy or thiocarboxy, and
When R ⁵ represents a carboxy group, the compounds of formula (I) may form esters. Such esterified groups represented by R ⁴ have the formula --C (: X ') X'R ⁶ or --A [-C (: X') X '.
R ⁶ ] n, and in the case of R ⁵ , is represented by the formula —COOR ⁶ .
In each of the above formulas, one of X ′ represents an oxygen atom and the other represents an oxygen atom or a sulfur atom. A represents a C ₁ -C ₅ alkylene group, an alkylidene group, an alkenylene group or an alkenylidene group, or when n is 1, these groups are the substituents specified in the alkyl group or alkenyl group of R ⁴ . One is shown. n is 1 or 2. R ⁶ is an alkyl group, a substituted alkyl group (the substitution is selected from the following group: halogen atom, cyano group, hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, phenoxy group, carboxylic group Containing at least one heteroatom selected from acid acyl group, epoxy group, carboxy group, (C ₁ -C ₆ alkoxy) carbonyl group, di (C ₁ -C ₆ alkyl) amino group, and nitrogen atom or oxygen atom to 5 or 6-membered heterocyclic ring group), C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group,
C ₃ -C ₈ cycloalkyl group, C ₃ -C ₈ cycloalkyl group having at least one C ₁ -C ₆ alkyl substituent, the aralkyl group, a substituted aralkyl group (the substituent is at least 1
Halogen atoms, C ₁ -C ₆ alkyl groups and nitro groups), phenyl groups, substituted phenyl groups (the substitution is at least 1 and is selected from the following groups: halogen atom, nitro group, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆
Alkanoyl group, (C ₁ -C ₆ alkoxy) carbonyl group,
Di (C ₁ -C ₆ alkyl) amino group, C ₁ -C ₆ alkanoylamino group and cyano group), di (C ₁ -C ₆ alkyl) amino group, or at least one selected from nitrogen atom and oxygen atom Is a 5- or 6-membered heterocyclic group containing a hetero atom of.

When R ⁶ represents an alkyl group, it can be straight-chain or branched-chain alkyl having 1 to 20 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t. -Butyl,
Pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, octadecyl and the like are preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable.

When R ⁶ represents a substituted alkyl group, the alkyl itself may be as described above, preferably a C ₁ -C ₄ alkyl group. Examples of the substituted alkyl group include, for example, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trichloroethyl, 2-dianoethyl, 2-hydroxyethyl, 4-hydroxybutyl, 2,3-dihydropropyl. , Ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-
Propoxyethyl, 2-ethylthioethyl, 2-phenoxyethyl, 2-benzoyloxyethyl, 2-acetoxyethyl, 2,3-epoxypropyl, carboxymethyl, 2-carboxyethyl, ethoxycarbonylmethyl, 2-diethylaminoethyl, 2- Dimethylamino-
1-methylethyl, 3-pyridylmethyl, oxolane-
2-ylmethyl and the like can be mentioned. Among the above substituted alkyl groups, at least one halogen, C ₁ -C ₄ alkoxy, C ₁
-C ₄ alkylthio or (C ₁ -C ₄ alkoxy) C ₁ -C ₄ alkyl group having a carbonyl substituent is preferred.

When R ⁶ represents an alkenyl group, it preferably has 3 or 4 carbon atoms and is, for example, allyl, methallyl or 2-butenyl.

When R ⁶ represents an alkynyl group, it preferably has 3 or 4 carbon atoms and is preferably 2-propynyl.

When R ⁶ is a cycloalkyl group or a substituted cycloalkyl group, the cycloalkyl itself preferably has 5 or 4 carbon atoms, most preferably cyclohexyl or 2
-Methylcyclohexyl.

When R ⁶ represents an aralkyl group or a substituted aralkyl group,
The aralkyl group itself is preferably benzyl, phenethyl or phenylpropyl, most preferably benzyl, 4-methylbenzyl, 4-nitrobenzyl, 4-
Chlorbenzyl, phenethyl or 3-phenylpropyl.

When R ⁶ represents a substituted phenyl group, it is preferably 2-
Chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,3,4-trichlorophenyl, 2,3,5-trichlorophenyl, 2,4,6-trichlorophenyl, 3,4,5-trichlorophenyl, 2-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3, 5-dimethylphenyl,
2-chloro-6-methylphenyl, 4-chloro-2-methylphenyl, 4-chloro-3-methylphenyl, 2,4
-Dichloro-6-methylphenyl, 2,6-dichloro-4
-Methylphenyl, 4-chloro-3,5-dimethylphenyl, 4-chloro-2-nitrophenyl, 2-chloro-4
-Nitrophenyl, 4-chloro-3,5-dimethyl-6-
Nitrophenyl, 2-allylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-formylphenyl, 4-acetylphenyl, 4-methoxycarbonylphenyl, 4-butoxycarbonylphenyl, 3-dimethylaminophenyl, 4 -Acetylaminophenyl and 4-cyanophenyl.

When R ⁶ represents a dialkylamino group, it is preferably
Dimethylamino, diethylamino or dipropylamino.

When R ⁶ represents a heterocyclic group, it is a 5 or 6 membered ring and contains at least one of the group consisting of nitrogen and carbon atoms. When the heterocycle itself is substituted, the substituent is preferably ₁ to 3 C ₁ -C ₄ alkyl. Examples of substituted or unsubstituted heterocycles are, for example, 5-methylisoxazol-3-yl, 2-pyrimidyl, 2-pyridyl, 3-pyridyl and 1-methyl-
3-piperidyl may be mentioned.

If in the compound of formula (I) R ⁴ represents a carboxy group, a thiocarboxy group, or an alkyl or alkenyl group containing one or two carboxy or thiocarboxy, it may form an acid halide. The acid halide has the formula (I) in which R ⁴ has the formula CX ″ · Hal or −
When represented by A (-CX ", Hal) n, A and n have the same meanings as described above, X" represents an oxygen atom or a sulfur atom, and Hal represents a halogen atom, especially It represents chlorine, fluorine, bromine or iodine, preferably chlorine or bromine.

R ⁴ represents a carboxy group, a thiocarboxy group, or an alkyl or alkenyl group containing 1 or 2 carboxy or thiocarboxy, and R ⁵
When is a carboxy group, the compound of formula (I) may form an acid amide.

That is, in the formula (I), R ⁴ represents a group CX ″, NR ⁷ R ⁸ , especially —CO, NR ⁷ R ⁸ or a group —A (CX ″, NR ⁷ R ⁸ ) n, or R ⁵ represents group -CO, the case showing an NR ⁷ R ^8. In the above formulas, A, X ″ and n have the same meanings as described above.
R ⁷ represents a hydrogen atom, C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or a C ₂ -C ₆ alkenyl group. R ⁸ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a substituted C ₁ -C ₆ alkyl group (has at least one substituent selected from the following group: halogen atom, cyano group, hydroxyl group, C _1- C ₆ alkoxy group, phenoxy group, phenoxy group having at least one halogen substituent, carboxy group, (C ₁ -C ₆ alkoxy) carbonyl group, di (C ₁ -C ₆ alkyl) amino group and nitrogen atom and oxygen at least a heteroatom selected from atoms heterocyclic group having 5 or 6-membered ring containing one), C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, C ₃ -C ₈ cycloalkyl group, Have at least one C ₁ -C ₆ alkyl substituent
C ₃ -C ₈ cycloalkyl group, an aralkyl group, a substituted aralkyl group (the substituent is at least one halogen atom,
C ₁ -C ₆ alkyl group and nitro group), a phenyl group, a substituted phenyl group (the substitution is at least 1).
Halogen atom, hydroxyl group, nitro group, cyano group, C _1-
C ₆ alkyl group, trifluoromethyl group, is selected from C ₁ -C ₆ alkoxy and (C ₁ -C ₆ alkoxy) carbonyl group), a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkanoyl oxy, C ₁ -C ₆ alkanoyl group, C ₁ -C ₆ alkanoyl group having at least one C ₁ -C ₆ alkoxy substituents of, (C ₁ -C ₆ alkoxy) thiocarbonyl group, (C ₁ -C ₆
An alkyl) thiocarbamoyl group, a phenylthiocarbamoyl group, a phenylthiocarbamoyl group containing at least one halogen substituent in the phenyl moiety, an amino group,
A di (C ₁ -C ₆ alkyl) amino group, an anilino group or a 5- or 6-membered heterocyclic group containing at least one hetero atom selected from a nitrogen atom, a sulfur atom and an oxygen atom, or , R ⁷ and R ⁸ form a piperidino group or a morpholino group together with the nitrogen atom to which they are bound.

In the above groups -CX ", NR ⁷ R ⁸ and -CO, NR ⁷ R ⁸ , -NR
^{The 7} R ⁸ moiety is preferably amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, t-butylamino, pentylamino, hexylamino, 3-chloropropylamino. , Dimethylamino, diethylamino, dipropylamino, diisopropylamino, ethylbutylamino, 2-chloroethylamino, cyanomethylamino, 2-cyanoethylamino, hydroxymethylamino, 2-hydroxyethylamino, 2-hydroxyethyl (methyl) amino , 2-hydroxyethyl (ethyl) amino, di (2-hydroxyethyl) amino, 2,3,
4,5,6-pentahydroxyhexyl (methyl) amino,
2-methoxyethylamino, 2- (2,6-dichlorophenoxy) ethylamino, carboxymethylamino, methoxycarbonylmethylamino, 2- (dimethylamino)
Ethylamino, 2- (diisopropylamino) ethylamino, 3- (dimethylamino) propylamino, 2-morpholinoethylamino, allylamino, diallylamino, 2-propynylamino, cyclopentylamino, cyclohexylamino, 2,3-dimethylcyclohexylamino , Benzylamino, 4-chlorobenzylamino, 4
-Nitrobenzylamino, 4-methylbenzylamino,
Phenethylamino, α, α-dimethylbenzylamino,
Anilino, 4-chloroanilino, 3,4-dichloroanilino, 3-chloro-2-hydroxyanilino, 2-hydroxyanilino, 3-hydroxyanilino, 4-hydroxyanilino, 4-nitroanilino, 4-methylanilino, 2, 6-dimethylanilino, 2,6-diethylanilino,
2,6-diisopropylanilino, 3-trifluoromethylanilino, 4-cyanoanilino, 2-methoxyanilino, 3-methoxyanilino, 4-methoxyanilino, 2
-Ethoxyanilino, 3-ethoxyanilino, 4-ethoxyanilino, 2-methoxycarbonylanilino, hydroxyamino, methoxyamino, acetoxyamino, 3
-Pyridylmethylamino, 4-pyridylmethylamino,
Formyl (methyl) amino, methoxyacetyl (methyl) amino, methoxythiocarbonylamino, 3-methylthioureido, 3- (4-chlorophenyl) thioureido, hydrazino, 1-methylhydrazino, 2-dimethylhydrazino, 2-phenyl. It may be hydrazino, acetohydrazino, piperidinoamino, morpholinoamino, 2-pyrimidylamino, 2-pyridylamino, 3-pyridylamino, 4-pyridylamino, 2-thiazolylamino, piperidino or morpholino, more preferably amino, (C ₁ -C ₆ alkyl). amino, (C ₁ -C ₆ alkoxy)
Amino or morpholino amino.

In the compounds of formula (I), those in which R ⁴ is an alkyl or alkenyl group having one or two hydroxyl or mercapto groups are alcohols or thiols and are therefore capable of forming esters with acids. The same applies when R ⁴ is an alkyl group having a hydroxyimino group. These compounds are represented by the formula (I) in which R ⁴ is a group -A.
(X ″ R ⁹ ) n or a group —A═N—OR ⁹ is represented by the formula:
X ″ and n are as defined above, and R ⁹ represents an acyl group derived from carboxylic acid, sulfonic acid or phosphoric acid.

If R ⁹ represents an acyl group derived from a carboxylic acid, it can be a fatty acid or an aromatic acyl group. The aliphatic acyl group preferably contains 1 to 7, more preferably 2 to 4 carbon atoms and can be alkanoyl, haloalkanoyl, alkoxyalkanoyl or alkoxycarbonyl. Suitable alkanoyl groups are, for example:
Formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, trichloroacetyl, trifluoroacetyl,
Examples thereof include methoxyacetyl, methoxycarbonyl and ethoxycarbonyl. The aromatic acyl group is preferably an arylcarbonyl group and the aryl is preferably a phenyl group, selected from C ₁ -C ₄ alkyl (eg methyl, ethyl, t-butyl) and halogen (eg chlorine). It may have 1 to 3 substituents. Suitable aromatic acyl groups are benzoyl, toluoyl and o-, m- or p-chlorobenzoyl.

When R ⁹ is an acyl group derived from sulfonic acid, it is preferably an alkanesulfonyl group, such as metalsulfonyl and ethanesulfonyl.

When R ⁹ is an acyl group derived from phosphoric acid, it is preferably a di (C ₁ -C ₃ alkoxy) phosphoryl group, such as dimethoxyphosphoryl and diethoxyphosphoryl.

R ⁴ has an amino group having one or two aliphatic carboxylic acid acyl substituents, an aliphatic carboxylic acid acyl group, or one or two aliphatic carboxylic acid acyl substituents
When it is a C ₁ -C ₄ alkyl group or a C ₂ -C ₄ alkenyl group, and when R ⁵ represents an acyl group, the acyl group is
It is preferably selected from the aliphatic acyl groups described above, especially those exemplified as the groups represented by R ⁹ .

Other preferable examples of the acyl carboxylate represented by R ⁴ are 1
Further, two (C ₁ -C ₄ alkoxy) carbonyl, for example, a C ₁ -C ₆ alkanoyl group and a C ₃ -C ₆ alkenoyl group having a methoxycarbonyl or ethoxycarbonyl substituent, such as 2,2-di ( Ethoxycarbonyl) acetyl and 2,2-di (ethoxycarbonyl) pent-4-enoyl.

When R ⁴ represents a heterocyclic group, the number of atoms constituting the ring is preferably 3 to 6, more preferably 3, 5 or 6,
At least one of them is a hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Preferably 1, 2, 3 or 4 of the ring atoms are heteroatoms. The heterocycle itself may be substituted and, if substituted, is preferably 1 to 3 C ₁ -C ₄ alkyl substituents (eg methyl, ethyl, propyl, butyl etc. Are preferred).

Examples of the heterocyclic group represented by R ⁴ include, for example, a dioxolanyl group (preferably 1,3-dioxolanyl, more preferably 1,3
-Dioxolan-2-yl), an oxiranyl group, an oxazolinyl group (preferably 2-oxazolinyl group), an oxazinyl group and a dihydro analog thereof (preferably 1,3
-Oxazinyl, more preferably 1,3-oxazine-2-
And analogs thereof, such as 4,5-dihydro-1,3-oxazin-2-yl), oxadiazolyl groups and alkyl- and / or oxo-substituted oxadiazolyl groups (particularly 1,3,4- and 1,2 , 4-Oxadiazolyl and their substitutions such as 1,3,4-
Oxadiazol-2-yl, 2-methyl-1,3,4-oxadiazol-5-yl and 5-oxo-1,2,4-
Oxadiazol-3-yl) and tetrazolyl group and alkyl-substituted tetrazolyl group (in particular, 1H-tetrazol-5-yl, 1-methyl-1H-tetrazol-5
-Yl and 2-methyl-2H-tetrazol-5-yl).

When R ⁴ represents a C ₂ -C ₄ alkenyl group or a substituted C ₂ -C ₄ alkenyl group, or when R ⁵ represents a C ₂ -C ₄ alkenyl group, the alkenyl group is preferably vinyl or allyl. 1
-Propenyl, isopropenyl, 1-butenyl, 2-butenyl or 3-butenyl, more preferably vinyl, 1-propenyl or 1-butenyl.

When R ⁴ represents a substituted C ₁ -C ₄ alkyl group, the alkyl group is preferably methyl, ethyl, propyl, isopropyl, butyl, isoptyl, sec-butyl or t-butyl, more preferably Methyl, ethyl or propyl.

When R ⁴ or R ⁵ represents a halogen-substituted alkyl group, the halogen atom is preferably fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine.

When R ⁴ represents an alkyl or alkenyl group having a di (C ₁ -C ₃ alkyl) phosphono substituent, said substituent is preferably selected from those given for R ⁴ .

When R ⁴ represents an alkyl group having a heterocyclic substituent, the heterocyclic group is preferably the one represented by R ⁶ , and in this case, more preferably, an azolyl group, that is, at least one A 5-membered ring containing a nitrogen atom as a hetero atom, most preferably imidazolyl or 1,2,4-triazolyl.

When R ⁵ represents an alkyl group having at least one C ₁ -C ₃ alkoxy substituent, the alkoxy group is preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy or t-butoxy.

When R ⁵ represents an alkyl group having at least one aryl or aryloxy substituent, and when R ⁵ represents an aryl group, the aryl group is an aromatic carbocyclic group (preferably phenyl or naphthyl, more preferably Phenyl), which may have 1 to 3 halogen atoms (especially chlorine or bromine) and substituents selected from C ₁ -C ₄ alkyl groups (especially methyl or ethyl).

When R ⁵ represents an alkyl group having at least one C ₁ -C ₄ alkylamino substituent, said substituent is preferably methylamino, ethylamino, propylamino, butylamino or t-butylamino. .

When R ⁵ represents a C ₃ -C ₈ cycloalkyl group or a C ₂ -C ₄ alkynyl group, these suitable groups are the same as the corresponding groups shown for R ⁶ .

When R ⁵ represents an acyl group, the acyl is derived from carboxylic acid, sulfonic acid or phosphoric acid, suitable examples of which are:
It is the same as the corresponding group shown in R ⁹ .

If R ¹ , R ² , R ³ or R ⁵ represents a C ₁ -C ₆ alkyl group, this may be straight-chain or branched, preferably having 1 to 4 carbon atoms, For example methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, pentyl, isopentyl, hexyl and 2,2-
Examples include dimethylbutyl and the like. Of these, methyl, ethyl, isopropyl and sec-butyl are more preferred. Most preferred for R ¹ and R ² are R ¹ and
When R ² is both isopropyl, and R ¹ is ethyl
This is the case when R ² is sec-butyl.

If R ¹ and R ² represent a C ₂ -C ₆ alkenyl radical, this may be straight-chain or branched and preferably have 3 or 4 carbon atoms, for example allyl, methallyl,
Examples include 1-methylpropenyl and 2-butenyl.

When R ³ represents a halogen atom, it means chlorine, bromine,
It can be fluorine or iodine. However, it is most preferred that R ³ is hydrogen.

Among the compounds of the present invention, preferable ones are represented by the following formula (II).

In the above formula (II), R ¹ , R ² and R ³ have the same meanings as described above, and R ⁴ a is a group —CO.R ³⁰ .-CO.X ″ R ¹¹ , —A—
^{COX "R 31, -CONR 7 R} 8, -A-CONR 7 R 8, -A-NHR 32, -A
—X ″ R ³³ , —A—R ³⁴ , a cyano group or a heterocyclic group.

When R ⁴ a is a group -CO.R ^30, R ³⁰ is a hydrogen atom or a halogen atom (preferably fluorine, chlorine, bromine or iodine) indicates, more preferably chlorine or bromine.

In the group —CO.X ″ R ¹¹ , X ″ represents an oxygen atom or a sulfur atom, R ¹¹ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an organic amine residue or R ^6. Indicates either group.

R ¹¹ is an alkali metal, an alkaline earth metal, a trivalent metal,
When it is an ammonium group or an organic amine residue, the compound of the present invention forms a salt.

Suitable salts include alkali metal salts such as sodium salt, potassium salt, alkaline earth metal salts such as calcium salt, magnesium salt, trivalent metal salts such as iron salt, aluminum salt, ammonium salt, trimethylamine salt. , Organic amine salts such as triethylamine salt, tripropylamine salt and tributylamine salt.

Examples of other suitable groups represented by R ¹¹ are the same as those set forth above for R ⁶ .

When R ⁴ a represents a group —A—COX ″ R ³¹ , A and X ″ have the same meanings as defined above, R ³¹ represents a hydrogen atom or C ₁ -C
₆ Indicates an alkyl group.

In the group -CO.NR ⁷ R ⁸ and ^{-A-CONR 7 R 8, A} , R 7 and R ⁸ have the same meanings as above, are as described above also for these examples.

When R ⁴ a represents a group —A—NHR ³² , A has the same meaning as defined above, preferably a C ₁ -C ₄ alkylene group, R 4
³² is a phenyl group or C ₁ -C ₄ alkyl or (C ₁ -C ₆
A phenyl group having an alkyl) carbamoyl substituent is shown.

If R ⁴ a is a group -A-X'R ^33, shall apply the same meaning as X "and A are described above, A is the preferred C ₁ -C ₄ alkylene group, R ³³ is hydrogen atom, C ₁ -C ₆ alkanoyl group, C ₁ -C ₆ haloalkanoyl, benzoyl or C ₁
-C shows a ₆ alkyl group.

When R ⁴ a represents a group —A—R ³⁴ , A is as defined above, preferably a C ₁ -C ₄ alkylene group, R ³⁴
Represents a halogen atom, a cyano group or a C ₁ -C ₆ alkanoyl group.

When R ⁴ a represents a heterocyclic group, it is preferably an oxiranyl group, a 1,3,4-oxadiazol-2-yl group or a 5-oxo-1,2,4-oxadiazole- group. A 3-yl group is shown.

In formulas (I) and (II), R ⁴ and R ⁴ a are preferably both attached at the 3-position.

In the above formula (II), a particularly preferred compound has R ⁴ a of 3
Bound to the position, and the group -COR ³⁰ ,, -CO.X "R ¹¹ ,, -A
-COX "R ³¹ , -CO.NHR ⁸ , -A-CONHR ⁸ , -AX" R ³³ ,-
A-R ³⁴ , cyano group or 1,3,4-oxadiazole-2
-Yl group (X "represents an oxygen atom or a sulfur atom, R ¹¹
Is a hydrogen atom, a C ₁ -C ₁₀ alkyl group or a phenyl group, R ⁸ is a hydrogen atom or a C ₁ -C ₆ alkyl group, and A is
C ₁ -C _{4 represents an} alkylene group or an alkenylene group, and R ³⁰
Represents a hydrogen atom, and R ³⁴ has the same meaning as defined above).

The most preferred compounds of formula (I) and formula (II) are
R ³ represents a hydrogen atom, R ¹ and R ² are the same and represent an ethyl group or an isopropyl group, or R ¹ represents an ethyl group and R ² represents a sec-butyl group. , And R ⁴ a represents a particularly preferred group as described above.

The compounds of the present invention are exemplified below. The number assigned to each compound is referred to as it is in the following description.

Among the above compounds, preferred ones are compound No. 9,11,65,75,
77,78,81,82,83,84,85,86,153,278,279,280,295,323,32
9,332,338,346,365 and 393.

The compounds of the present invention can be prepared by any of the methods described below.

Production Process A The compound of the present invention in which R ⁴ is a carboxy group, a thiocarboxy group (preferably a mercaptocarbonyl group) or a nitro group, that is, a compound having the formula (Ia) and a nitro derivative thereof are represented by the following reaction schemes. Can be manufactured by.

In the formula, R ¹ , R ² , R ³ and X ′ have the same meanings as described above.

Step A1 is a step of reacting compound (IV) which is a derivative of phthalic anhydride with compound (III) which is a derivative of aniline, and can be carried out in the presence or absence of a solvent. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit the reaction, but it is preferably an aromatic hydrocarbon such as toluene or xylene, an aprotic polar solvent such as dimethylformamide or dimethylsulfoxide. , Methyl butyl ketone, methyl isobutyl ketone,
Mention may be made of ketones such as cyclohexanone, butanol and acetic acid.

Although it is desirable to heat the reaction, it is usually a by-product during the reaction, so an azeotrope with water and an inert solvent are used,
Preference is given to carrying out the reaction at the boiling point of this azeotrope.

Usually and preferably, after the end of step A1, step A2 is carried out under the same reaction conditions as step A1 without isolating compound (V) as an intermediate.

However, depending on the purpose, the intermediate (V) can be isolated and can usually be obtained quantitatively. For example, compound (IV) in which the carboxy group in which X'represents an oxygen atom is substituted at the 3-position and 2.6-diethylaniline or 2.6
-In the reaction with diisopropylaniline, a melting point of 24
Corresponding intermediates (V) with 3.5-244 ° C. or melting points 191-193 ° C. respectively can be obtained.

Further, instead of using the phthalic anhydride derivative of compound (IV), phthalic acid itself corresponding to compound (IV) or an acid halide (eg chloride or bromide), active amide, active ester (eg p-nitrobenzyl ester) It is also possible to use active derivatives such as

Process B The compound (Ib) in which R ⁴ represents a —CX ″ .R ¹⁰ group in the compound (I) can be produced by reacting the halogenating reagent with the corresponding compound (Ia).

(In the formula, R ¹ , R ² , R ³ , R ¹⁰ and X ″ have the same meanings as described above.) The halogenating reagent is not particularly limited, and is generally a reagent capable of producing an acid halide from a carboxylic acid. I can, but
Preferably thionyl chloride or thionyl bromide is used.

The reaction is carried out according to a conventional method, but it is preferable to carry out the reaction in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but preferably it is an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene, or a aliphatic hydrocarbon such as cyclohexane. Cyclic hydrocarbons are used. The reaction temperature is not particularly limited and may be carried out in a wide temperature range, but preferably,
The reaction is carried out by heating under reflux.

Process C Compounds (Ic) and (I) which are ester and amide derivatives of carboxylic acid or thiocarboxylic acid of compound (Ia)
c ′) can be produced from the corresponding acid halide (Ib) according to the following reaction scheme.

In the formula, R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and X ″ have the same meanings as described above.

Compound (Ic) and compound (Ic ′) can be prepared by reacting compound (Ib) with compound (VI) or (VII),
You can get each. The two reactions are carried out under similar reaction conditions and will therefore be described together below.

The reaction is preferably carried out in the presence of a deoxidizing agent, preferably also a solvent. The deoxidizer is used to remove the acid generated by the reaction from the reaction solution, and a base is usually used. Preferred are tri-linear alkylamines such as tetraethylamine and tributylamine, tertiary cycloalkylamines such as 1,5-diazabicyclo [5.4.0] undecene-5, pyridine, or sodium carbonate and potassium carbonate. Such alkali metal carbonates. The solvent is not particularly limited as long as it does not inhibit the reaction, but is preferably aromatic hydrocarbons such as benzene and toluene, chloroform, halogenated hydrocarbons such as methylene chloride, diisopropyl ether, diethyl ether, Tetrahydrafuran,
Ethers such as dioxisan, acetonitrile, nitriles such as propionitrile, ketones such as acetone, or a mixture of two or more of the above solvents is used.

Process D The compound (Id) in which R ⁴ is a cyano group in the compound (I)
Can be produced by dehydrating compound (VIII) according to a conventional method.

(In the formula, R ¹ , R ² and R ³ have the same meanings as described above.) The dehydrating agent is not particularly limited, and is generally a reagent capable of converting an acid amide into a corresponding nitrile. As long as it does not affect, phosphorus pentachloride, thionyl chloride or phosphorus oxychloride is preferably used, and phosphorus oxychloride is more preferable.

It is preferable to use a solvent for the reaction, and the solvent is not particularly limited as long as it does not inhibit the reaction, but preferably an aliphatic hydrocarbon such as hexane and heptane, an aromatic such as benzene, toluene and xylene. Group hydrocarbons, alicyclic hydrocarbons such as cyclohexane, or halogenated hydrocarbons such as chloroform and methylene chloride are used. The reaction temperature can be selected within a wide range, but it is usually preferable to carry out the reaction under heating under reflux.

The compound (VIII), which is the starting material of the production method D, is the compound (I
In c ′), R ⁷ and R ⁸ are hydrogen atoms and X ″ is a carbon atom, and this compound can be produced according to the method described in the production method C.

Production Method E A compound (I) in which R ⁴ represents a hydroxymethyl group, a halomethyl group, an alkoxymethyl group, a cycloalkoxymethyl group, an aryloxymethyl group, an alkenyloxymethyl group or an alkynyloxymethyl group (I
e), (Ie ′) and (Ie ″) can be produced according to the following reaction formula.

In the above formula, Ar is the formula Hal represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom or a bromine atom, and R ¹² is cycloalkyl in the definition of R ^5. An alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an optionally substituted alkyl group are shown.

In compound (Ib), compound (IX) in which X ″ represents an oxygen atom and R ¹⁰ represents a chlorine atom is a starting material for this reaction, but can be produced by the method described in production method B, if desired.

Step E1 is a step of reducing the chloroformyl group of compound (IX) to a hydroxymethyl group. Generally, the reducing agent may be any one that can be used to reduce the chloroformyl group,
Preference is given to using hydrogenated complex metals such as lithium aluminum hydride, lithium borohydride, sodium bis (2-methoxyethoxy) aluminium hydride, sodium borohydride. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but is preferably tetrahydrofuran, diethyl ether, ethers such as diclime, aromatics such as benzene and toluene. Hydrocarbons. The reaction temperature is not particularly limited, but usually the reaction is carried out at a high temperature so that side reactions do not occur. The reaction is preferably carried out under ice cooling to room temperature. If desired, the synthesized compound (Ie) is treated with Step E2.
In, it can be converted to the corresponding halomethyl derivative (Ie ′). This step can be achieved by reacting compound (Ie) with a halogenating reagent such as thionyl chloride, thionyl bromide or phosphorus tribromide. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but preferably hexane,
Aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene, toluene, xylene, alicyclic hydrocarbons such as cyclohexane or diethyl ether,
Ethers such as tetrahydrofuran and dioxane. The reaction temperature is not particularly limited and a wide range of temperatures can be selected, but the reaction is preferably carried out at room temperature or the boiling point of the reaction mixture.

If desired, the synthesized compound (Ie ′) is a corresponding cycloalkoxymethyl, aryloxymethyl, alkenyloxymethyl, alkynyloxymethyl, alkoxymethyl or substituted alkoxymethyl derivative (Ie ″).
Can be converted to. It has the formula (Ie ′)
It can be achieved by reacting with a compound having R ¹² OH (wherein R ¹² has the same meaning as described above), but is preferably a corresponding metal alkoxide, more preferably an alkali such as sodium alkoxide. It is usually carried out by using a metal alkoxide and heating. The reaction is preferably carried out in a solvent, preferably an excess of R ¹² OH is used as solvent, especially when R ¹² OH is a lower alcohol.

Process F Compound (Ie) is converted to the corresponding ester by reacting with a suitable reactive derivative of an acid such as an acid anhydride, an acid mixed anhydride, an active ester or an acid halide.
Acid halides are preferably used, and more preferably acid chlorides or bromides are used. When an acid halide is used, a deoxidizer is preferably used to remove hydrogen halide formed during the reaction. The deoxidizing agent is not particularly limited, but preferably triethylamine, tributylamine, tertiary amines such as 1,5-diazabicyclo [5.4.0] undecene-5, pyridine, or sodium carbonate,
Alkali metal carbonates or alkaline acid carbonates such as potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are used. The reaction is preferably carried out in a solvent,
The solvent is not particularly limited as long as it does not inhibit the reaction,
Preferable examples are aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers such as diisopropyl ether, diethyl ether, tetrahydrofuran and dioxane, acetonitrile and propionitrile. Nitriles or ketones such as acetone are used.
The reaction can be carried out over a wide temperature range, but is preferably carried out under ice-cooling to the boiling point of the reaction mixture.

Process G In the compound (I), a compound in which R ⁴ represents a methyl group substituted with a di (C ₁ -C ₃ alkoxy) phosphorylthio group is
Compound (Ie ') can be prepared by reacting a metal compound having the formula M-S-R ⁹ a. In the formula, M
Represents an alkali metal, preferably sodium or potassium, and R ⁹ a represents a dialkoxyphosphoryl group defined in R ⁹ above.

The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but preferably, ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile, or a ketone such as acetone. It is a kind. The reaction temperature is not particularly limited, but is usually room temperature.

Process H The compound (Ih), (I in which R ⁴ represents an aminomethyl group or variously substituted aminomethyl group in the compound (I)
h ′), (Ih ″), (Ih) and (Ih ′) can be produced according to the following reaction formula.

In the above formula, Ar has the same meaning as described above, R ¹³ represents a hydrogen atom or various alkyl groups, substituted alkyl groups, cycloalkyl groups or aryl groups defined in R ⁵ , and R ¹⁴
Represents a hydrogen atom or an alcohol residue of an ester, and R
¹⁵ is a group that bonds to a carbonyl group, and is a group that represents a carboxylate acyl group defined by R ⁹ when expressed as a -COR ¹⁵ group, R ¹⁶ is a group that bonds to a sulfonyl group, and -SO ₂ R ¹⁶
When expressed as a group, it is a group showing the sulfonate acyl group defined by R ⁹ above, and R ¹⁷ is the group or atom defined by R ⁷ or R ⁸ .

Step H1 is a step of reacting the halomethyl compound (Ie ′) with a primary amine having the formula R ¹³ NH ₂ in the presence of a deoxidizing agent. As the deoxidizing agent, those described in the production method F are used. The equivalent relationship between the compound (Ie ′) and the primary amine is not particularly limited, but the equivalent ratio of the primary amine and the compound (Ie ′) is preferably selected in the range of 1: 1 to 3: 1. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons, preferably chloroform, Aliphatic halogenated hydrocarbons such as methylene chloride or ethers such as tetrahydrofuran and dioxane. The reaction can be carried out over a wide temperature range, but is preferably carried out at room temperature to 80 ° C.

Steps H2, H3 and H4 respectively react the compound (Ih) synthesized by Step H1 with a compound having the formula Hal.COOR ¹⁴ , a compound having the formula R ¹⁵ COHal or a compound having the formula R ¹⁶ SO ₂ Hal. It is a process. The reaction is preferably carried out in a solvent using a deoxidizing agent at room temperature or under heating. As the solvent and the deoxidizing agent, those described in Process F are used, and the reaction temperature is preferably room temperature to 50 ° C.

Step H5 is a step of reacting the compound (Ih) with appropriate isocyanates having the formula R ¹⁷ NCO to produce the compound (Ih). The reaction method is usually carried out at room temperature in a solvent with a catalytic amount of a base, preferably pyridine. As the solvent, those described in Process F are used.

Process J Compound (X) is (In the formula, Ar represents the same meaning as described above, R ¹⁸ and R ¹⁹ represent a heterocyclic group containing a nitrogen atom together with a nitrogen atom, and such a group is as defined in the definition of R ⁴ . A heterocyclic group described as a substituent in the substituted alkyl group section), a compound (Ie ′) defined in Processes E and H is added to a heterocyclic group having the formula NHR ¹⁸ R ¹⁹ Medium, R ¹⁸
And R ¹⁹ are as defined above. ) And can be manufactured. The reaction is preferably carried out in a solvent in the presence of a deoxidizing agent. As such a deoxidizing agent, those described in Process F can be used, but alkali metal carbonates are preferably used. The solvent is not particularly limited as long as it does not inhibit the reaction, but ethers such as dioxane or nitriles such as acetonitrile are preferable. The reaction is preferably carried out at room temperature or under heating.

Process K In compounds (I), compounds (Ik), (Ik '), (Ik) in which R ⁴ represents a formyl group, a hydroxyiminomethyl group, a cyclic acetal group or a methyl group substituted with an alkoxy, alkenyloxy or alkynyloxy group. ″) And (Ik) can be produced according to the following reaction formula.

In the above formula, Ar has the same meaning as described above, R ²⁰ represents an alkyl group, an alkenyl group or an alkynyl group defined in R ⁵ , and R ²¹ represents a formula And R ²¹ together represent a heterocyclic group defined by R ⁴ , and R ²¹ itself preferably represents an optionally branched alkylene group.

Step K1 is a step of reacting the compound (Ie) produced by the production method E with an oxidizing agent to produce a corresponding formyl derivative (Ik). The oxidizing agent is not particularly limited as long as it can convert a hydroxymethyl group into a formyl group,
Preferably manganese dioxide or chromic anhydride,
It is preferable to use 1 to 6 equivalents relative to compound (Ie). The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but preferably lower fatty acids such as acetic acid or halogenated compounds such as chloroform, carbon tetrachloride and methylene chloride. Hydrocarbons. The reaction is usually carried out at room temperature or under heating.

Step K2 is a step of reacting (Ik) synthesized above with hydroxylamine in a suitable solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but alcohols such as methanol and ethanol are preferable. The reaction is usually carried out at room temperature or under heating.

Step K3 is a step of reacting compound (Ik) with an optionally branched alkylene glycol, preferably in the presence of a catalytic amount of p-toluenesulfonic acid. The reaction is preferably carried out in a solvent, but the solvent is not particularly limited as long as it does not inhibit the reaction, and aromatic hydrocarbons such as benzene, toluene and xylene are preferable. The reaction is usually carried out under heating.

Step K4 is a step of reacting compound (Ik) with a compound having the formula CH (CR ²⁰ ) ₃ , preferably compound CH (CR ²⁰ )
_{Use 3} in excess. The reaction is preferably carried out at room temperature in the presence of catalytic amounts of p-toluenesulfonic acid. The reaction is preferably carried out in a solvent, but the compound CH (CR ²⁰ ) ₃ is preferably used in excess as a reaction solvent.

Process L The compound (XI) in which R ⁴ in the compound (I) represents a group having two carboxylate acyl substituents is (In the formula, Ar has the same meaning as described above, and R ¹⁵ has the same meaning as defined in the description of the production method H.), the compound (Ie ′) and the compound (XII) defined in the production method E. It can be produced by reacting with.

(In the formula, R ¹⁵ has the same meaning as described above.) The reaction is Organic
Synthesis 42 , 75 (1962), by heating in acetone solvent in the presence of potassium carbonate.

Process M The compounds (Im), (Im ′) and (Im ″) in which R ⁴ represents variously substituted alkyl groups in the compound (I) can be produced according to the following reaction scheme.

In the above formula, R ⁶ , R ⁷ , R ⁸ , Ar and Hal have the same meanings as above,
R ¹⁴ has the same meaning as defined in the production method, R ²² represents a hydrogen atom or a C ₁ -C ₄ alkyl group, and m represents 0 or 1.

Step M1 is a step of producing the compound (Im) by reacting the compound (Ie ′) synthesized in the production method E with a cyanide, preferably an alkali metal cyanide (eg sodium cyanide or potassium cyanide). The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, and preferably ethanol, alcohols such as tetrahydrofurifurol alcohol, glycols such as ethylene glycol, ethylene glycol. Glycol ethers such as monomethyl ether,
Amides such as dimethylformamide or dimethylsulfoxide. The reaction is usually carried out at room temperature or under heating.

If desired, compound (Im) can be converted to the corresponding acid or ester compound (Im ′) in which m is 0 by heating in the presence of a strong acid such as sulfuric acid. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but alcohols such as methanol and ethanol are preferable. Corresponding esters can be obtained when alcohols are used as solvents. The reaction is usually carried out under heating.

Further, the compound (Im ′) in which m is 1 can be produced by subjecting the corresponding compound (XIII) to hydrogenation, preferably catalytic reduction. Compound (XIII) can be synthesized based on the production method P described below. The hydrogenation reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but alcohols such as methanol and propanol, lower fatty acids such as tetrahydrofuran or acetic acid are preferred. Is. The hydrogenation reaction is preferably carried out using a metal catalyst such as palladium on carbon or palladium-barium sulphate while introducing hydrogen.

If desired, the compound in which R ¹⁴ in compound (Im ′) represents an alcohol residue of the ester can be converted into the corresponding carboxylic acid in step M4. Preferably compound (Im ') is achieved by using an acid in a solvent. Preferably, the solvent is an ether such as dioxane and the acid is a strong mineral acid such as sulfuric acid or hydrochloric acid. The reaction is usually carried out at room temperature or under heating.

Step M5 is a step of converting the compound (Im ″) into a corresponding acid halide, and is carried out under the same reaction conditions according to the method described in the production method B.

Steps M6 and M7 produce the corresponding compound (Im ″ ″) by reacting the acid halide (Im) with a compound having the formula HNR ⁷ R ⁸ or reacting with a compound having the formula R ⁶ SH The corresponding thio compound (Im ″ ″ ′)
Is a process for producing the compound, and can be similarly performed according to the reaction conditions described in the process C.

Process N In the compound (I), compounds in which R ⁴ represents various substituted alkyl group, alkenyl group or acyl group of carboxylic acid can be produced according to the following reaction formula.

In the above formula, Ar is as defined above, R ²³ is a hydrogen atom, C
₁ -C ₄ alkyl group, a nitro group or an aliphatic acyl group.

Step N1 is the compound (Ik) synthesized in the above production method K.
Is a Grignard reagent having the formula R ²³ CH ₂ MgHal (wherein R ²³
Represents a hydrogen atom or a C ₁ -C ₄ alkyl group, and Hal has the same meaning as described above, but is preferably a bromine atom. ). The reaction is usually performed at room temperature or under cooling. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, and ethers such as diethyl ether and tetrahydrofuran are preferable.

In the compound (In), a compound in which R ²³ represents a nitro group is a formyl compound (Ik) and nilotromethane.
ll.Chem.SOc.Japan, 41, 1444 (1968), it can be produced in step N2 by reacting according to the method.

A compound in which R ²³ represents an aliphatic acyl group in the compound (In) can also be produced in Step N3 by reacting the formyl compound (Ik) with an aldehyde or ketone having the formula CH ₃ —COR ^23. . The reaction is usually performed in a solvent in the presence of a base such as sodium hydroxide at room temperature. The solvent is not particularly limited as long as it does not inhibit the reaction, but preferably alcohols such as methanol and ethanol, ethers such as diethyl ether and tetrahydrofuran, benzene, toluene, hexane,
Hydrocarbons such as heptane or ketones such as acetone are more preferable, and a mixed solvent of acetone and water is more preferable.

If desired, the synthesized hydroxy compound (In) can be converted to the corresponding alkenyl compound (In ') in step N4. This step is a step of reacting the compound (In) with a suitable dehydrating agent such as P-toluenesulfonic acid. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but aromatic hydrocarbons such as benzene and toluene are preferable. The reaction is usually carried out under heat. If desired, the synthesized compound (In ′) can be converted into the corresponding epoxy compound (In ″) by reacting it with an oxidizing agent in Step N5. The oxidizing agent generally has an ethylene type double bond. There is no particular limitation as long as it can be exchanged with an epoxy group, but m-chloroperbenzoic acid or perbenzoic acid is preferred.The reaction is preferably carried out in a solvent, and the solvent may be any one which does not inhibit the reaction. Although not particularly limited, halogenated hydrocarbons such as chloroform and methylene chloride are preferable, and the reaction temperature and the reaction time vary depending on various factors, but when m-chloroperbenzoic acid is used. Usually, the reaction is carried out at room temperature or under heating at 50 ° C or lower.

Further, if desired, the synthesized hydroxy compound (In) can be converted into an acyl compound (In) by oxidizing the compound. The reaction conditions, the reaction reagents and the solvent are the production method
The method is the same as the method described in step K1 in.

Process P The compounds (Ip) and (Ip ') in which R ⁴ is a substituted alkenyl group in the compound (I) can be produced according to the following reaction scheme.

In the above formula, Ar has the same meaning as described above, R ²² has the same meaning as defined in the manufacturing method M, and R ²⁴ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, or the like. a shows a C ₁ -C ₄ alkyl group.

Step P1 is a step of treating compound (XIV) with a strong base such as sodium hydride to generate a carbanion, and reacting this with compound (Ik) at room temperature or under heating.

(In the formula, R ²² and R ²⁴ have the same meanings as described above, and three R ²⁴ in the above formula may be the same or different.) The two reactions can be carried out successively in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but ethers such as diethyl ether and tetrahydrofuran or dimethylformamide are preferable.

If desired, the synthesized compound (Ip) can be hydrolyzed and converted into the corresponding acid (Ip ′). The reaction is usually carried out in an appropriate solvent using an acid at room temperature or under heating.

Process Q In compound (I), R ^{4 is} di (alkoxycarbonyl)
Compounds (Iq) and (Iq ′) showing a substituted acyl group can be produced according to the following reaction formula.

In the above formula, Ar, Hal and R ²⁴ have the same meanings as described above, R ²⁵
Represents an organic group, preferably the above-mentioned optionally substituted alkyl group, alkenyl group or alkynyl group.

In step Q1, the compound (XV) synthesized according to the production method B has the formula R ²⁴ OMgCH
It is a step of reacting with a Grignard compound having (COOR ²⁴ ) ₂ . In the formula, R ²⁴ has the same meaning as above, and three R 3
²⁴ may be the same or different. This Grignard reagent is synthesized according to the method described in Org.Syn.Col.Vol.IV, 708 (1963). The reaction is usually carried out under heating in a suitable solvent.

If desired, the synthesized compound (Iq) can be converted to compound (Iq ′) by reacting with a compound having the formula R ²⁵ Hal, for example, 2-propenyl bromide. The reaction is usually carried out by heating in the presence of a base such as an alkali metal carbonate (eg sodium carbonate or potassium carbonate). The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but ethers such as dioxane and nitriles such as acetonitrile are preferable.

Production Method R The compound (Ir) in which R ⁴ represents a di (C ₁ -C ₃ alkoxy) phosphoryl-substituted methyl group in the compound (I) includes a compound (Ie ′) synthesized in the production method E and a trialkylphosphite. It can be usually produced by reacting at 90 to 100 ° C.

(In the formula, Ar has the same meaning as described above, and R ²⁶ represents a C ₁ -C ₃ alkyl group.) Trialkyl phosphite is usually preferably used in excess with respect to compound (Ie ′).

A compound in which R ⁴ represents a dialkoxyphosphoryl-substituted alkyl group (C ₂ or higher alkyl group) can be similarly produced from a raw material having a corresponding halogenated alkyl group.

Process S The compound (Is) in which R ⁴ represents a mercaptomethyl group in the compound (I) is the compound (Ie ′) synthesized in the process E.
And a thiol compound having the formula R ⁵ SH can be prepared by reacting in a suitable solvent.

The thiol compound (wherein Ar and R ⁵ are as defined above) is preferably reacted in the form of a metal thiolate, more preferably an alkali metal thiolate such as sodium thiolate. The solvent is not particularly limited as long as it does not inhibit the reaction, but alcohols such as ethanol, ketones such as acetone or ethers such as tetrahydrofuran are preferable. The reaction temperature is not particularly limited, but it is usually preferable to carry out the reaction at room temperature.

Production Method T Compounds (It) and (It ′) in which R ⁴ represents an N ² -hydroxyamidino group or an acylcahydroxyamidino group in Compound (I) are the cyano compound (Id) and hydroxylamine synthesized in Production Method D, respectively. React
Further, it can be produced by acylating if desired.

(Wherein Ar and R ²⁴ have the same meanings as described above) The reaction is preferably carried out in a solvent, preferably using a lower alcohol such as methanol, usually at room temperature or under heating, and Get (It). This one also has the formula Hal.CO
The compound (It ′) is obtained by reacting a compound having OR ²⁴ with a ketone such as acetone as a solvent in the presence of a deoxidizing agent. Suitable deoxidizers are those described in Process F, but in this case particularly preferred ones are
Alkali metal carbonates or organic amines such as triethylamine.

Process U The compound (I) in which R ⁴ represents an amino group or a mono- or diacylamino group is produced by converting the nitro group of the compound (XVI) into an amino group and optionally acylating the amino group. be able to.

The first step is a step of reacting a nitro compound (XVI) with a metal or a metal chloride in a mixed solution of an acid and a solvent.
The preferred metal is zinc, iron or tin and the preferred metal chloride is stannic chloride. Suitable acids are acetic acid or hydrochloric acid and suitable solvents are alcohols such as ethanol or ethers such as dioxane, tetrahydrofuran.

The amino compound can also be obtained by catalytic reduction of compound (XVI). A preferable catalyst is palladium carbon, and it is preferable to carry out the reaction in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but alcohols such as methanol and ethanol are preferable.

The amino compound thus synthesized has, for example, the formula R ²⁴ COHal
Can be converted to an amino derivative by reacting the compound having ## STR5 ## with a deoxidizing agent, preferably in the presence of a suitable solvent. As the deoxidizing agent and the solvent, those described in the production method F are preferably used, and the reaction is usually carried out at room temperature or under heating. The starting material (XVI) is prepared according to the method described in Process A.

Process V The compound (Iv) in which R ⁴ represents a specific heterocyclic group in the compound (I) is prepared by combining the compound (XVII) with a deoxidizing agent in J. Org. Chem.
It can be produced by reacting according to the method described in 39, 2787 (1974).

(In the formula, Ar has the same meaning as described above, P represents an integer of 2 to 4, and is preferably 2 or 3.) A suitable deoxidizing agent is an alkali metal carbonate such as potassium carbonate. The reaction is preferably carried out in a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction, but preferably benzene,
Aromatic hydrocarbons such as toluene or ketones such as acetone. The starting material (XVII) is prepared for the method described in Preparation C.

Production Method W The compound (Iw) in which R ⁴ represents an oxadiazolyl group in the compound (I) can be produced by reacting the compound (XVIII) with a dehydrating agent, usually under heating.

(Wherein Ar and R ²⁴ have the same meanings as described above). Suitable dehydrating agents are phosphorus oxychloride, thionyl chloride or phosphorus pentoxide, particularly preferably phosphorus oxychloride. The dehydrating agent is preferably used in excess.

Process X The compound (Ix) in which R ⁴ is an unsubstituted oxadiazolyl group in the compound (I) is produced by reacting the compound (XIX) with a suitable ring-closing reagent capable of inserting one carbon atom. can do.

(In the formula, Ar has the same meaning as described above.) Suitable ring-closing reagents are orthochloroformates such as ethyl orthochloroformate or formaldehyde (used in the form of formalin or paraformaldehyde), and orthochloroformic acid is particularly preferable. Esters are preferred. The ring-closing reagent is usually used in an excess amount, and the reaction is preferably carried out under heating.

Process Y The compound (Iy) in which R ⁴ represents an oxo-substituted oxadiazolyl group in the compound (I) can be produced by reacting the compound (XX) with a base in a suitable solvent at room temperature. .

(In the formula, Ar has the same meaning as described above, and R ²⁷ represents a leaving group.) Suitable leaving groups represented by R ²⁷ include C ₁ -C ₄ lower alkoxy such as methoxy, ethoxy, butoxy. A group, an aryloxy group such as phenoxy, benzyloxy or an aralkoxy group, or a halogen atom such as a chlorine atom. Suitable bases are alkali metal alkoxides such as sodium methoxide, alkali metal hydrides such as sodium hydride or metal hydroxides (preferably alkali metal hydroxides such as sodium hydroxide). When sodium alkoxide is used as the base, the corresponding alcohol is preferably used as the reaction solvent.

Process Z The compounds (Iz) and (Iz ′) in which R ⁴ in the compound (I) may be substituted with R ⁴ can be produced according to the following reaction formula.

In the above formula, Ar and R ²⁴ have the same meanings as described above. The starting material (Id) is manufactured according to the method described in Process D.

Step Z1 is a step of reacting compound (Id) with an azide such as sodium azide in a suitable solvent at room temperature or under heating. The solvent is not particularly limited as long as it does not inhibit the reaction, but preferably, aromatic hydrocarbons such as benzene and toluene, ethers such as petroleum ether, tetrahydrofuran, dioxane and diethyl ether, or dimethylfoxide or It is a polar solvent such as dimethylformamide. After the reaction, the compound (Iz) can be usually obtained in the form of a metal salt corresponding to the azide salt used in the reaction, but the free compound (Iz) can be obtained by treating with an acid such as hydrochloric acid or sulfuric acid. be able to. The alkylated compound (Iz ′) can be synthesized by reacting the compound (Iz) with an alkylating agent in a suitable solvent using a deoxidizing agent. As the deoxidizing agent, those described in the production method F are used, and sodium carbonate is preferable. Suitable alkylating agents are alkyl iodides such as methyl iodide, dialkyl sulphates such as dimethyl sulphate, trialkyl phosphates, P-toluene sulphonic acid alkyl esters or trifluoroacetic acid alkyl esters. . The reaction is usually carried out under heating.

After the various reactions described above, the desired compound can be purified from the reaction solution according to a conventional method. If it is necessary to carry out two or more reactions in succession, it is also possible to carry out the reactions in the same reactor without isolating the intermediate.

The compounds of formula (I) show therapeutic and protective effects against plant diseases by soil application or application as agricultural fungicides. In particular, it is effective against root-knot disease that has occurred in cruciform plants and has been difficult to control. In addition, it is effective against rice blight, which is an important disease of rice cultivation, or against seedling blight of various crops such as peat, cotton and cucumber caused by Rhizoctonia and ring-spot of tomato.

The compound of the present invention is mixed with a carrier and, if necessary, other auxiliary agents, and has a formulation form usually used as an agricultural fungicide, for example, powder, coarse powder, fine granule, granule, wettable powder, emulsion. , Prepared as a suspending agent, a water solvent, etc. The carrier as used herein refers to a synthetic or mixed agent which is mixed in an agricultural fungicide in order to help the accessibility of the active ingredient compound to the site to be treated and to facilitate the storage, transportation or handling of the active ingredient compound. It means a natural inorganic or organic substance.

Suitable solid carriers include clays typified by kaolinite group, montmorillonite group or attabardite group, talc, mica, pyrophyllite, pumice, vermiyukilite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium. Inorganic substances such as lime, apatite, zeolite, anhydrous silicic acid, synthetic calcium silicate, soybean powder,
Tobacco flour, walnut flour, wheat flour, wood flour, starch, vegetable organic substances such as crystalline cellulose, coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum,
Examples thereof include synthetic or natural polymer compounds such as dammalgam, waxes such as carnauba wax and beeswax, and urea.

Suitable liquid carriers include paraffin or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalene, carbon tetrachloride and chloroform. , Trichlorethylene,
Monochlorobenzene, chlorinated hydrocarbons such as o-chlorotoluene, ethers such as dioxane and tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone and isophorone, ethyl acetate, amyl acetate, ethylene glycol acetate, Esters such as diethylene glycol acetate, dibutyl maleate, diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether , Ether alcohols such as diethylene glycol butyl ether,
Examples include polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

The surfactants used for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, fluidity improvement, rust prevention, etc. are nonionic, anionic, cationic and Either zwitterionics can be used, but usually nonionic and / or anionic ones are used. Suitable nonionic surfactants include, for example:
Those obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol, those obtained by polymerizing addition of ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol, and alkyls such as butylnaphthol and octylnaphthol. Polymerization addition of ethylene oxide to naphthol, polymerization addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, oleic acid, polymerization addition of ethylene oxide to mono- or dialkyl phosphoric acid such as stearyl phosphoric acid and dilauryl phosphoric acid. Those obtained by polymerizing addition of ethylene oxide to amines such as dodecylamine and stearic acid amide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene Those obtained by polymerizing addition Kishido, such as those obtained by polymerizing addition of ethylene oxide and propylene oxide. Suitable anionic active surfactants include, for example, sodium lauryl sulfate, alkyl sulfate salts such as trail alcohol sulfate amine salt, sodium sulfosuccinate dioctyl ester, 2
-Alkyl sulfonates such as sodium ethylhexene sulfonate, sodium isopropyl naphthalene sulfonate, sodium methylene bis naphthalene sulfonate,
Examples thereof include aryl sulfonates such as sodium lignin sulfonate and sodium dodecylbenzene sulfonate.

Further, the agricultural fungicide of the present invention improves the properties of the preparation, and in order to enhance the biological effect, casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polymers such as polyvinyl alcohol. Compounds and other auxiliaries such as activated carbon, cyclodextrin, solid paraffin or higher fatty acids such as stearic acid can also be used in combination.

The above carriers and various auxiliary agents are appropriately used alone or in combination depending on the purpose in consideration of the dosage form of the preparation, the application scene, and the like.

Dusts usually contain, for example, 0.1 to 25 parts by weight of the active ingredient compound, and the balance is a solid carrier.

The wettable powder usually contains, for example, 5 to 90 parts by weight of the active ingredient compound, and the rest is a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a thixotropic agent, a defoaming agent and the like are added.

Granules usually contain, for example, 0.1 to 35 parts by weight of the active ingredient compound, and the rest are mostly solid carriers. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.05 to 1.7 mm.

The emulsion usually contains, for example, 5 to 50 parts by weight of the active ingredient compound, contains about 5 to 20 parts by weight of an emulsifier, and the balance is a liquid carrier, and other auxiliary agents are added if necessary. .

The agricultural fungicide of the present invention thus prepared in various dosage forms is sprayed on the foliage of the crop, or applied to the soil or the water surface, for example, before or after the occurrence of the disease on the crop in the field or the paddy field. At this time, the disease can be effectively controlled by throwing 1 to 5000 g, preferably 10 to 1000 g, as an active ingredient per 10a.

Further, when the agricultural fungicide of the present invention is used for seed treatment, for example, as a seed dressing agent, 0.01% to 2%, preferably 0.1 to 0.5%, as an active ingredient per seed weight, is effectively applied by dressing. Can control soil or seed-borne diseases.

The agricultural bactericide of the present invention preferably contains other agricultural bactericide in order to broaden the bactericidal spectrum, and in some cases, a synergistic effect can be expected.

Examples of such other fungicides include, for example, thiophanate, thiophanate methyl, benomyl, carbendazole, hymexazole, teclophthalam, chlorothalonil, fuentin hydroxide, captan,
Captafol, salam, edifenphos, tricyclazole, IBP, PCNB, fusalide, kasugamycin,
Vinclozolin, Procymidone, Isoprothiolane, Probenazole, Pyroquilone, Clobentazone (S-19
01), metalaxyl, eclomezole, iprodione,
Propiconazole, Etaconazole, Triadimefone,
Prochloraz, 4-methylsulfonyloxyphenyl, N-methylthiol carbamate (NK-191), N
Examples thereof include, but are not limited to, bactericides such as-(1-butoxy-2,2,2-trichloroethyl) salicylamide (NK-483). In addition, other insecticides such as isoxathion, phennitrothion, if necessary,
Diazinon, trichlorfon, disulfoton, acephate, carbaryl, bropoxure, mesomil,
Thiocyclam, cartap, pyrethrin, allethrin,
Fumbalerate, etc., and also appropriately mixed with acaricide, herbicide, plant growth regulator, nematicide, bactericide, soil improver, improving material, paper pot, synthetic soil, fertilizer or chemical fertilizer etc. It can also be used. Next, a method for producing the compound having the formula (I) will be described with reference to Examples.

Example 1. 3-Carboxy-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 11) 1.92 g of trimellitic anhydride was added to 15 m of methyl isobutyl ketone.
After being dissolved in 1 by heating with stirring, 1.8 g of 2,6-diisopropylaniline was added, and a water separator was attached and the mixture was heated under reflux for 3 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude imide which was recrystallized from 30% water-containing ethanol to give a melting point of 274 to 275 ° C.
3 g of the target compound of

Example 2. 3-chloroformyl-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 44) 2 g of 3-carboxy-N- (2,6-diisopropylphenyl) phthalimide was suspended in 30 ml of benzene, Thionyl chloride (1.4 g) was added and the mixture was heated under reflux for 2 hours. The solvent and excess thionyl chloride were distilled off from the reaction mixture under reduced pressure to give a melting point of 148
2.1 g of the target compound at -150 ° C was obtained.

Example 3. N- (2,6-diisopropylphenyl) -3
-Methoxycarbonylphthalimide (Compound No. 65) 2 g of 3-chloroformyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 15 ml of benzene, 5 ml of methanol was added, and the mixture was heated under reflux for 2 hours. The crude crystals obtained after evaporation of the solvent were recrystallized from methanol to give a melting point of 173-1.
1.9 g of the target compound at 73.5 ° C was obtained.

Example 4. 3-carbamoyl-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 153) After dissolving 2 g of 3-chloroformyl-N- (2,6-diisopropylphenyl) phthalimide in 10 ml of tetrahydrofuran. Then, ammonia was added dropwise while stirring under ice cooling. After adjusting the pH of the reaction mixture to 7, the mixture was further stirred at room temperature for 1 hour. The reaction mixture was put into water, the target compound was extracted with ethyl acetate, separated and washed with water. After drying with mirabilite, the solvent was distilled off under reduced pressure, and the obtained crude amide was recrystallized from methanol to obtain 1.8 g of the desired compound having a melting point of 251-252 ° C.

Example 5. 3-Cyano-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 258) 2.3 g of 3-carbamoyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 5 ml of dichloroethane, 1 ml of phosphorus oxychloride was added, and the mixture was heated under reflux for 2 hours with stirring. After allowing to cool, the reaction mixture was poured into ice water, the target compound was extracted and extracted with ethyl acetate and washed with water. After drying with mirabilite, the solvent was distilled off under reduced pressure, and the resulting crude nitrile was recrystallized from n-hexane to give 1.8 g of the desired compound having a melting point of 162-163 ° C.
Got

Example 6. N- (2,6-diisopropylphenyl) phthalimide-3-carboxylic acid sodium salt (Compound No. 3
2) 2 g of 3-carboxy-N- (2,6-diisopropylphenyl) phthalimide in 0.15 ml of tetrahydrofuran.
39 g of sodium ethoxide was added to the solution, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the solvent and ethanol produced during the reaction were distilled off under reduced pressure to obtain 2.1 g of the target compound having a melting point of 345 ° C or higher.

Example 7. Tris [N- (2,6-diisopropylphenyl) phthalimide-3-carboxylic acid] aluminum salt (Compound 266) N- (2,6-diisopropylphenyl) phthalimide-
2-Carboxylic acid sodium salt 2 g tetrahydrofuran 15
dissolved in ml. 0.24 g of this in 5 ml of tetrahydrofuran
A solution in which aluminum chloride was dissolved was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the precipitated sodium chloride was removed and the solvent of the solution was evaporated under reduced pressure to obtain 1.9 g of the desired compound having a melting point of 300 ° C or higher.

Example 8. N- (2,6-diisopropylphenyl) -3
-Hydroxymethylphthalimide (Compound 280) To a solution prepared by dissolving 1.05 g of 3-chloroformyl-N- (2,6-diisopropylphenyl) phthalimide in 8 ml of tetrahydrofuran, 65 mg of lithium boron hydride was added, and the mixture was added at room temperature to 20%. Stir for minutes. After the reaction is complete, add 2
It was poured into 10 ml of normal hydrochloric acid and extracted with ethyl acetate. The extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain crude crystals.
By recrystallizing from benzene, melting point 187-189 ° C
0.85 g of the target compound of

Example 9. N- (2,6-diisopropylphenyl) -3
-Isobutyryloxymethylphthalimide (Compound number
286) 1 g of N- (2,6-diisopropylphenyl) -3-hydroxymethylphthalimide was dissolved in 30 ml of acetonitrile, 0.5 g of isobutyryl chloride and 0.45 g of triethylamine were added thereto at room temperature for 6 hours. It was stirred. After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate.
The extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give crude crystals.
Recrystallized from a 1: 1 mixture of benzene and hexane, melting point 158
0.82 g of the desired compound at ˜159 ° C. was obtained.

Example 10.3-Bromomethyl-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 307) 2 g of N- (2,6-diisopropylphenyl) -3-hydroxymethylphthalimide was dissolved in 50 ml of diethyl ether. 0.54 g of phosphorus tribromide was added to and stirred at room temperature for 5 hours. After completion of the reaction, the reaction solution was poured into water and extracted with diethyl ether. The extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give crude crystals. Wash the crystals with methanol, dry,
2.3 g of the target compound having a melting point of 201-202 ° C. was obtained.

Example 11. N- (2,6-diisopropylphenyl) -3-
Methoxymethylphthalimide (Compound No. 291) 1.2 g of 3-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 10 ml of methanol, and 162 mg of 28% sodium methoxide-methanol solution was added thereto and heated for 4 hours. Refluxed. After completion of the reaction, the reaction solution was cooled, poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (5:
Purified by developing with the solvent of 1), melting point 128-129
0.7 g of the target compound at ℃ was obtained.

Example 12 3-Aminomethyl-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 308) 2 g of 3-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 100 ml of methylene chloride and cooled. With stirring, 1 g of ammonia was added, and the mixture was stirred at room temperature for 2 days. After completion of the reaction, the reaction solution was washed with a saturated aqueous sodium chloride solution until neutralized, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals are washed with hexane and dried to give a melting point of 135-1.
1.75 g of the target compound at 37.5 ° C was obtained.

Example 13. 3-Cyclohexylaminomethyl-N- (2,6
-Diisopropylphenyl) phthalimide (Compound number
312) 1 g of 3-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 20 ml of methylene chloride, and 0.28 g of cyclohexylamine and 0.28 g of triethylamine were dissolved in this.
Was added and stirred for 6 hours. After the completion of the reaction, the same treatment as in Example 12 was carried out to obtain 0.72 g of the desired compound having a melting point of 148 to 149 ° C.

Example 14. N- (2,6-diisopropylphenyl) -3-
Methoxyacetamide methylphthalimide (Compound number
316) 0.7 g of 3-aminomethyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 5 ml of methylene chloride, 0.24 g of methoxyacetyl chloride and 0.28 g of triethylamine were added, and the mixture was stirred at room temperature for 3 hours. . After the reaction was completed, the reaction solution was poured into water and extracted with methylene chloride. The extract solution was washed with water and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography and purified by developing with a solution of hexane-ethyl acetate (2: 1),
0.75 g of the desired compound having a melting point of 167-168 ° C was obtained.

Example 15. N- (2,6-diisopropylphenyl) -3-
(1-Imidazolylmethyl) phthalimide (Compound number
319) 1 g of 3-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 50 ml of acetonitrile, and 204 mg of imidazole and 1.7 g of potassium carbonate were added to this solution,
Heated to reflux for hours. After cooling the reaction solution, it was poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was distilled off. The residue was purified by subjecting it to silica gel column chromatography and developing with ethyl acetate to obtain 0.62 g of the desired compound having a melting point of 216-218 ° C.

Example 16. N- (2,6-diisopropylphenyl) -3-
Formylphthalimide (Compound No. 323) 1 g of N- (2,6-diisopropylphenyl) -3-hydroxymethylphthalimide was dissolved in 25 ml of chloroform,
7 g of activated manganese dioxide was added thereto, and the mixture was stirred at 70 ° C. for 3 hours. After cooling the reaction solution, excess manganese dioxide was removed, and the solution was dried under reduced pressure. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (7:
Purified by developing with the solution of 3), melting point 158.5-15
0.8 g of the target compound at 9.5 ° C was obtained.

Example 17. N- (2,6-diisopropylphenyl) -3-
Hydroxyiminomethylphthalimide (Compound No. 32
6) 1 g of N- (2,6-diisopropylphenyl) -3-formylphthalimide was dissolved in 20 ml of methanol, to which 0.5 g of hydroxylamine hydrochloride was added at room temperature and stirred for 2 hours. After the reaction was completed, the reaction solution was dried under reduced pressure. The residue was subjected to silica gel column chromatography and purified by developing with a solution of hexane-ethyl acetate (4: 1), melting point 232-
0.67 g of the target compound at 234 ° C was obtained.

Example 18. N- (2,6-diisopropylphenyl) -3-
Dimethoxymethylphthalimide (Compound No. 327) 1 g of N- (2,6-diisopropylphenyl) -3-formylphthalimide, 5 ml of methyl orthoformate and 0.1 g of P-toluenesulfonic acid were mixed and stirred at room temperature for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was evaporated to give crude crystals. Recrystallization from benzene gave 1 g of the desired compound having a melting point of 154-157 ° C.

Example 19. N- (2,6-diisopropylphenyl) -3-
(1,3-Dioxolan-2-yl) phthalimide (Compound No. 328) 1 g of N- (2,6-diisopropylphenyl) -3-formylphthalimide was added to 3 ml of ethylene glycol and 50 m of toluene.
0.1 g of p-toluenesulfonic acid was added thereto, and the mixture was heated under reflux for 3 hours. After cooling the reaction solution, pour it into water,
It was extracted with ethyl acetate, the extract was washed with water and the solvent was distilled off under reduced pressure to give crude crystals. Recrystallized from benzene, melting point 189.
0.81 g of the desired compound having a temperature of 5 to 190.5 ° C was obtained.

Example 20. 3- (2,2-Diacetylethyl) -N- (2,6-
Diisopropylphenyl) phthalimide (Compound No. 35)
0) 2-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide (2 g) was mixed with acetylacetone (2 g) and acetone (50 g).
2 ml of potassium carbonate, and the mixture was heated under reflux for 3 hours. The reaction solution was cooled and then poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was distilled off to obtain crude crystals. Recrystallized from hexane-ethyl acetate (9: 1), mp 146-149
1.43 g of the target compound (° C.) was obtained.

Example 21-Cyanomethyl-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 346) 0.15 g of sodium cyanide was dissolved in 3 ml of dimethyl sulfoxide, and 3-bromomethyl-N- (2,6-diisopropyl) was added thereto. 1 g of phenyl) phthalimide was added, and the mixture was stirred at 50 ° C. for 10 minutes. The reaction mixture was poured into water and extracted with ethyl acetate, the extract was washed with water and the solvent was distilled off. The residue was subjected to silica gel column chromatography and purified by developing with a solvent of hexane-ethyl acetate (8: 1), melting point 206-
0.6 g of the target compound at 209 ° C was obtained.

Example 22. N- (2,6-diisopropylphenyl) -3-
Ethoxycarbonylmethylphthalimide (Compound No. 33
2) 0.8 g of 3-cyanomethyl-N- (2,6-diisopropylphenyl) phthalimide, 1 ml of concentrated sulfuric acid and 5 ml of ethanol
Were mixed and heated under reflux for 5 hours. The reaction solution was cooled, poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was distilled off under reduced pressure. The residue was purified by subjecting it to silica gel column chromatography and developing with hexane-ethyl acetate (7: 1) to obtain 0.66 g of the desired compound having a melting point of 160-162 ° C.

Example 23. N- (2,6-diisopropylphenyl) -3-
(2-Ethoxycarbonylethyl) phthalimide (Compound No. 338) 2.18 g of N- (2,6-diisopropylphenyl) -3- (2-ethoxycarbonylvinyl) phthalimide (Compound of Example 31) is dissolved in 25 ml of ethyl acetate. Then, 0.4 g of 5% palladium carbon was added to this, and catalytic reduction was carried out at room temperature under normal pressure. Palladium carbon was pressed, and the liquid was concentrated under reduced pressure to obtain crude crystals. Recrystallized from acetone, melting point 133-1
1.7 g of the target compound at 34.5 ° C was obtained.

Example 24. 3- (2-Carboxyethyl) -N- (2,6-
Diisopropylphenyl) phthalimide (Compound No. 33)
0) N- (2,6-diisopropylphenyl) -3- (2-ethoxycarbonylethyl) phthalimide (0.65 g), dioxane (20 ml) and 1N sulfuric acid (15 ml) were mixed and heated under reflux for 4 hours. The reaction solution was cooled, poured into water and extracted with ethyl acetate,
The extract was washed with water and the solvent was evaporated under reduced pressure to give crude crystals.
The crystals were washed with hexane and dried to obtain 0.51 g of the desired compound having a melting point of 183-185 ° C.

Example 25. N- (2,6-diisopropylphenyl) -3-
(1-hydroxyethyl) phthalimide (Compound No. 35
1) Dissolve 1 g of N- (2,6-diisopropylphenyl) -3-formylphthalimide in 60 ml of diethyl ether, add 4 ml of 1 mol of methylmagnesium bromide-tetrahydrofuran solution to the solution at room temperature while stirring under ice cooling. It was stirred for 2 hours. After the reaction was completed, 6N hydrochloric acid and ethyl acetate were added, the organic layer was separated, washed with water, and the solvent was evaporated.
The residue was purified by subjecting it to silica gel column chromatography and developing with a solution of hexane-ethyl acetate (3: 1) to obtain 0.7 g of the desired compound having a melting point of 166-167 ° C.

Example 26. N- (2,6-diisopropylphenyl) -3-
(1-Hydroxy-2-nitroethyl) phthalimide (Compound No. 354) N in 20 ml of isopranol containing 0.87 g of potassium fluoride
-(2,6-Diisopropylphenyl) -3-formylphthalimide (1 g) was added and dissolved, and nitromethane (1.83) was added.
g was added and the mixture was stirred at room temperature for 5 hours. Remove insoluble matter,
The liquid was dried under reduced pressure. The residue was purified by subjecting it to silica gel column chromatography and developing with a solution of hexane-ethyl acetate (4: 1) to obtain 0.6 g of the desired compound having a melting point of 172-176 ° C.

Example 27. 3- (2-Acetyl-1-hydroxyethyl)
-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 353) N- (2,6-diisopropylphenyl) -3-formylphthalimide 1.34 g, acetone 4 ml and dioxane 10 ml
0.5N aqueous sodium hydroxide solution at room temperature
0.6 ml was added and stirred for 8 hours. The reaction mixture was poured into water, acidified with hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography and hexane-ethyl acetate (4: 1).
The product was purified by being developed in to obtain 1.2 g of the objective compound having a melting point of 170 to 176 ° C.

Example 28. 3-Acetyl-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 355) 0.5 g of N- (2,6-diisopropylphenyl) -3- (1-hydroxyethyl) phthalimide was added to 10 ml of chloroform.
, 1 g of manganese dioxide was added, and the mixture was heated under reflux for 4 hours. After cooling the reaction solution, manganese dioxide was removed and the solution was dried under reduced pressure. The residue was subjected to silica gel column chromatography, developed with hexane-ethyl acetate (4: 1) and purified to give 0.42 g of the desired compound having a melting point of 150-151 ° C.

Example 29. N- (2,6-diisopropylphenyl) -3-
Vinylphthalimide (Compound No. 360) 1 g of N- (2,6-diisopropylphenyl) -3- (1-hydroxyethyl) phthalimide, 0.3 g of p-toluenesulfonic acid and 30 ml of toluene were mixed and heated under reflux for 5 hours. The reaction solution was cooled, poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, developed with hexane-ethyl acetate (8: 1) and purified to obtain 0.45 g of the desired compound having a melting point of 60 to 61 ° C.

Example 30. N- (2,6-diisopropylphenyl) -3-
Oxiranylphthalimide (Compound No. 368) 0.4 g of N- (2,6-diisopropylphenyl) -3-vinylphthalimide, 1 g of m-chloroperbenzoic acid and 6 ml of methylene chloride were mixed and stirred at 50 ° C. for 16 hours. . The reaction solution was cooled, poured into water and extracted with methylene chloride, the extract was washed with water, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (1
When developed and purified at 0: 1), the target compound with a melting point of 84-86 ° C
0.18 g was obtained.

Example 31. N- (2,6-diisopropylphenyl) -3-
(2-Ethoxycarbonylvinyl) phthalimide (Compound No. 366) 0.74 g of triethylphosphonoacetate was dissolved in 10 ml of a 1: 1 mixture of tetrahydrofuran and dimethylsulfoxide, 0.144 g of sodium hydride was added, and the mixture was allowed to stand at room temperature for 15 minutes. It was stirred. Furthermore, N- (2,6-diisopropylphenyl)
1 g of -3-formylphthalimide was added and the mixture was stirred at 55-60 ° C for 20 minutes. The reaction solution was poured into water and extracted with ethyl acetate,
The extract was washed with water and the solvent was evaporated under reduced pressure to give crude crystals. Recrystallization from ethanol gave 0.84 g of the desired compound having a melting point of 131.5-132.5 ° C.

Example 32. 3-Di (ethoxycarbonyl) acetyl-N-
(2,6-Diisopropylphenyl) phthalimide (Compound No. 358) Magnesium (0.27 g) was added to absolute ethanol, 2 ml of anhydrous diethyl ether and 1.76 g of diethyl malonate were added, and the mixture was heated under reflux for 3 hours. While continuing heating, a solution prepared by dissolving 3.69 g of 3-chloroformyl-N- (2,6-diisopropylphenyl) phthalimide in 5 ml of tetrahydrofuran was added to this solution, and the mixture was heated under reflux for 1 hour. The reaction solution was cooled, poured into water, and extracted with ethyl acetate. The extract was washed with water and the solvent was evaporated under reduced pressure to give crude crystals. Recrystallization from ethanol gave 4.5 g of the desired compound having a melting point of 114-122.5 ° C.

Example 33 3- [2,2-di (ethoxycarbonyl) -4-
Pentenoyl] -N- (2,6-diisopropylphenyl) phthalimide (Compound No. 359) 3-di (ethoxycarbonyl) acetyl-N- (2,6-
1 g of diisopropylphenyl) phthalimide was dissolved in 30 ml of acetonitrile, 0.5 g of allyl bromide and 1 g of potassium carbonate were added, and the mixture was heated under reflux for 1 hour. The reaction solution was cooled, poured into water, and extracted with ethyl acetate. Wash the extract with water,
The solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, developed with hexane-ethyl acetate (9: 1) and purified to give the desired compound with a melting point of 106.5-107.5 ° C.
I got 25g.

Example 34. N- (2,6-diisopropylphenyl) -3-
Dimethoxyphosphorylmethylphthalimide (Compound number
369) 0.6 g of 3-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide and 2 ml of trimethylphosphite were mixed and stirred at 90 to 100 ° C. for 1 hour. Excess trimethylphosphite was distilled off under reduced pressure to obtain crude crystals.
Recrystallized from diisopropyl ether, melting point 133-134 ℃
0.46 g of the desired compound of

Example 35. 3-Diethoxyphosphorylthiomethyl-N-
(2,6-Diisopropylphenyl) phthalimide (Compound No. 370) 0.7 g of 3-bromomethyl-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 20 ml of acetone, and O, O-
0.36 g of diethyl thiophosphate-S-potassium salt was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography, developed with hexane-ethyl acetate (2: 1) and purified to obtain 0.6 g of the desired compound having a melting point of 80 to 82 ° C.

Example 36. N- (2,6-diisopropylphenyl) -3-
(N-hydroxyamidino) phthalimide (Compound number
375) Hydroxylamine hydrochloride 0.42g, methanol 20ml and 2
0.38 g of 8% sodium methoxide-methanol solution was mixed for 10 minutes. A solution prepared by dissolving 2 g of 3-cyano-N- (2,6-diisopropylphenyl) phthalimide in 30 ml of methanol was added thereto, and the mixture was stirred at room temperature for 2 hours. Under reduced pressure,
The solvent was evaporated, the residue was subjected to silica gel column chromatography, developed with hexane-ethyl acetate (2: 1), and purified to obtain 1.6 g of the desired compound having a melting point of 233 to 234 ° C.

Example 37. 3-Amino-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 382) 3.5 g of N- (2,6-diisopropylphenyl) -3-nitrophthalimide was dissolved in 30 ml of tetrahydrofuran and cooled with ice. did. A solution prepared by dissolving 9 g of stannous chloride in 8 ml of concentrated hydrochloric acid was added thereto with stirring, and stirring was continued for another 3 hours. The reaction solution was poured into water and sodium hydrogen carbonate was added to make the pH neutral. The precipitated solid was removed, and the solution was extracted with chloroform. The extract was washed with water and the solvent was distilled off to obtain crude crystals. Recrystallized from benzene containing a small amount of hexane,
2.8 g of the desired compound having a melting point of 266-267 ° C was obtained.

Example 38. 3-Acetamido-N- (2,6-diisopropylphenyl) phthalimide (Compound No. 385) 0.17 g of 3-amino-N- (2,6-diisopropylphenyl) phthalimide was dissolved in 10 ml of benzene to prepare acetyl bromide. 65 mg and triethylamine 53 mg were added, and the mixture was stirred at room temperature for 1 hour. Benzene was distilled off, and the residue was subjected to silica gel column chromatography, developed with hexane-ethyl acetate (1: 1) and purified to obtain 0.16 g of the desired compound having a melting point of 237 to 238 ° C.

Example 39. N- (2,6-diisopropylphenyl) -3-
(2-oxazolinyl) phthalimide (Compound No. 39
0) 0.5 g of 3- (2-chloroethylcarbamoyl) N- (2,6-diisopropylphenyl) phthalimide was added to 30 g of acetone.
It was dissolved in ml, 0.3 g of potassium carbonate was added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was distilled off under reduced pressure to give crystals. Recrystallization from ethanol gave 0.35 g of the desired compound having a melting point of 190-191 ° C.

Example 40. N- (2,6-diisopropylphenyl) -3-
(1,3,4-Oxadiazol-2-yl) phthalimide (Compound No. 393) N- (2,6-diisopropylphenyl) -3-hydrazinocarbonylphthalimide (1.5 g) and ethyl orthochloroformate (10 ml) were mixed, The mixture was heated under reflux for 10 hours. After cooling the reaction solution, it was poured into water and extracted with ethyl acetate. The extract was washed with water and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (5:
When developed and purified in 1), the target compound with a melting point of 141-142 ℃
0.8g was obtained.

Example 41. N- (2,6-diisopropylphenyl) -3-
(2-methyl-1,3,4-oxadiazol-5-yl)
Phthalimide (Compound No. 394) 3- (2-Acetylhydrazinocarbonyl) -N- (2,
1-g of 6-diisopropylphenyl) phthalimide (synthesized by using acetylhydrazine in place of ammonia in Example 4) and 7 ml of phosphorus oxychloride were mixed to give 100-
The mixture was heated and stirred at 110 ° C for 3 hours. After cooling the reaction mixture, Example 4
Treated in the same manner as in 0 to obtain 0.35 g of the desired compound having a melting point of 213 to 214 ° C.

Example 42. N- (2,6-diisopropylphenyl) -3-
(5-oxo-1,2,4-oxadiazol-3-yl)
Phthalimide (Compound No. 395) N- (2,6-diisopropylphenyl) -3- (N-ethoxycarbonyloxyamidino) phthalimide (Compound of Example 45), 10 ml of methanol and 0.1 g of sodium methoxide are mixed at room temperature. And stirred for 20 minutes. The reaction solution was poured into water, neutralized with hydrochloric acid, and extracted with ethyl acetate. The extract was washed with water, the solvent was distilled off, treated in the same manner as in Example 40, and the target compound having a melting point of 220 to 221 ° C.
I got 4g.

Example 43. N- (2,6-diisopropylphenyl) -3-
(1H-tetrazol-5-yl) phthalimide (Compound No. 396) 1.8 g of aluminum chloride, 2.64 g of sodium azide and 1.5 g of 3-cyano-N- (2,6-diisopropylphenyl) phthalimide were added in this order on ice. It was added to 30 ml of cold anhydrous tetrahydrofuran. Then, the reaction solution was heated under reflux for 5 hours. After cooling, it was poured into ice water and the pH was made neutral with hydrochloric acid. Extraction with ethyl acetate, washing with water and evaporation of the solvent gave crystals. Recrystallized from benzene, melting point 145-1
1.55 g of the target compound at 46 ° C was obtained.

Example 44. N- (2,6-diisopropylphenyl) -3-
(Methyl-1H-tetrazol-5-yl) phthalimide (Compound No. 269) N- (2,6-diisopropylphenyl) -3- (1H-tetrazol-5-yl) phthalimide 1 g was added to dioxane 20.
After dissolving in ml, 0.57 g of methyl iodide and 0.37 g of potassium carbonate were added, and the mixture was heated under reflux for 1 hour. After cooling the reaction solution, it was treated in the same manner as in Example 40 to obtain 0.42 g of the desired compound having a melting point of 196 to 197 ° C.

Example 45. N- (2,6-diisopropylphenyl) -3-
(N-Ethoxycarbonyloxyamidino) phthalimide (Compound No. 376) 0.5 g of N- (2,6-diisopropylphenyl) -3- (N-hydroxyamidino) phthalimide was dissolved in 20 ml of acetone to give 0.15 g of ethyl chloroformate. Triethylamine 0.1
4 g was added, and the mixture was stirred at room temperature for 3 hours. Remove insoluble matter,
The liquid was evaporated under reduced pressure. The residue is subjected to silica gel column chromatography, developed with methylene chloride and purified,
0.55 g of the target compound having a melting point of 111-112 ° C was obtained.

Next, formulation examples of the agricultural fungicide of the present invention will be given. In the text, all "parts" means "parts by weight".

Example 46. Dust agent 2.5 parts of the compound of Compound No. (11), 47.5 parts of talc, 47 parts of clay and 3 parts of white carbon were uniformly mixed in a mixer and pulverized with a hammer mill to obtain a dust agent.

Example 47. Powder 5 parts of a compound of compound number (153), activated carbon 25 parts, talc 3
0 part and 40 parts of clay were uniformly mixed in a mixer and pulverized with a hammer mill to obtain a continuous powder.

Example 48. Granular agent Kagalite No. 2 (pumice-based crushed granular material, made by Silver Sangyo)
77.5 parts were charged in a ribbon mixer with a jacket, and a solution prepared by dissolving 2.5 parts of the compound of the compound No. (11) prepared in advance in 20.0 parts of acetone was added while stirring and sufficiently mixed to uniformly adsorb. Pass steam through the jacket part of the ribbon mixer, volatilize and remove acetone while stirring,
A base particle having a compound number (11) adsorbed thereon was prepared.
Then, the temperature of the base particles was maintained at 50 to 60 ° C., and while stirring, 20.0 parts of a solid paraffin (mp 68 to 70 ° C.) melt was added to cover the surface of the base particles. When the coating was completed, water was passed through the jacket and cooled to obtain coated granules containing 2.5% of the main ingredient with reduced phytotoxicity.

Example 49. Granules In the same manner as in Example 7 except that stearic acid (mp64 to 70 ° C.) was used instead of the solid paraffin in Example 48, a phytotoxicity containing 2.5% of the compound of Compound No. (11) was controlled. A reduced coated granule was obtained.

Example 50. Granules Compound No. (258) 5 parts of compound, 20 parts of bentonite, 1 part of calcium lignin sulfonate and 74 parts of clay are mixed, kneaded with an appropriate amount of water and kneaded, and granulated by a screen extrusion granulator. After granulation, it was dried and sized to obtain granules.

Example 51. Wettable powder 50 parts of compound No. (166), white carbon 5
Parts, 5 parts of Solpol AC-2495G (trade name of Toho Chemical Co., Ltd.) and 40 parts of clay were uniformly mixed in a mixer and ground with a hammer mill to obtain a wettable powder.

Example 52. Emulsion 10 parts of the compound of Compound No. (81), 10 parts of xylene, 12 parts of Paracor PS-2 (trade name of Nippon Emulsifier Co., Ltd.) and 68 parts of cyclohexanone were mixed and uniformly dissolved to obtain an emulsion. .

Next, test examples showing the effect of the compound of the present invention as an agricultural fungicide will be given.

Example 53. Chinese cabbage root-knot control test (mixing with soil) Chinese cabbage roots affected with root-knot disease (pathogenic fungus Plasmodiophora brassicae) were ground and mixed into a soil to prepare a soil-root-killed soil. The test compound is applied to the soil contaminated with the pathogenic bacteria 1
The mixture was mixed at 2.5 ppm and put in a 300 ml pot, and seeds of Chinese cabbage seeds (variety Musou) were sown (5 seeds were sown in one pot, and one seed was made after emergence). After raising the seedlings in a greenhouse for 45 days, the seedlings were extracted and the degree of disease on the roots was investigated according to the following criteria, and the average disease degree of 5 pots per ward is shown in Table 1.

Degree of disease 0. No root knot epidemic degree of disease 1. Root nodules on the lateral roots are small but small 〃 2. Many small knuckles are formed on the lateral roots, or large root knots are 〃 3. Small root knots on the main root Make, the number of side roots is small 〃 4. Make a large root knot in the main root, Medium side root knot 〃 5. Make a lot of large root knots in the main root and side root In addition, in this test, we have formula (I) In addition to the compounds of the present invention, the following compounds A to M described in each of the publications cited in "Prior Art" were tested.

Compound A: N- (2,6-diethylphenyl) -2-methylphthalimide Compound B: N- (2,6-diethylphenyl) -3-methylphthalimide Compound C: N- (2,6-diisopropylphenyl) -2)
-Methylphthalimide Compound D: N- (2,6-diisopropylphenyl) -3
-Methylphthalimide Compound E: 2-chloro-N- (2,6-diethylphenyl) phthalimide Compound F: 3-chloro-N- (2,6-diethylphenyl) phthalimide Compound G: 2-chloro-N- (2,6-Diisopropylphenyl) phthalimide Compound H: 3-chloro-N- (2,6-diisopropylphenyl) phthalimide Compound J: N- (2,6-diethylphenyl) -2-methoxyphthalimide Compound K : N- (2,6-diethylphenyl) -3-methoxyphthalimide Compound L: N- (2,6-diisopropylphenyl) -2
-Methoxyphthalimide compound M: N- (2,6-diisopropylphenyl) -3
-Methoxyphthalimide Example 54. Chinese cabbage root-knot control test (stem and leaf spray) The soil contaminated with the root-knot fungus (Plasmodiophora brassicae) was put in a unglazed pot with a diameter of 9 cm, and Chinese cabbage seeds (various warriors) were sown and thinned after germination. Then, 5 pieces were made per bowl. The true leaf extraction stage and the 3-4 leaf stage were sprayed twice with 100 ppm of the supply chemical solution at a rate of 10 ml per pot, and the plant was cultivated in a greenhouse for 45 days. investigated. Table 2 shows the average degree of disease per share for two wards of one ward.

Example 55. Rice blast disease control test (preventive spraying) 3 pots of 50 ml were applied to rice seedlings (cultivar: Nihonbare) at the 4-5 leaf stage.
After spraying 300ppm of the reagent solution and leaving it at room temperature for 24 hours,
Put 4-5 grains of the red leaf cultivated with Rhizoctonia solani in advance on the stalks of the rice and move them to a humid chamber at 25-27 ° C. Height (c
m). The results are shown in Table 3.

Example 56. Control test of seedling wilt of cucumber (irrigated irrigation) Rhizoctoni seedling wilt (Rhizoctoni) cultivated in bran at 28 ° C for 2 weeks
a solani) is evenly mixed with the soil, this soil is put into a pot with a diameter of 12 cm, 20 seeds of cucumber (variety: Sagamihanjiro) are sown at a time, and then 250 ppm of the reagent solution from 3 / m ² Irrigated at a rate. The pots were kept in a greenhouse at 25 ° C. for 2 weeks, and the number of seedlings causing seedling wilt (number) was investigated. Three wards in one ward are shown, and the total value is shown in Table 4.

Example 57. Control test for tomato ring spot disease (preventive spraying) 3 spots 50 on 3 to 4 leaf stage tomato seedlings (cultivar: Fukuju No. 2)
300 ppm of the reagent solution was sprinkled onto a ml. The next day, spraying inoculation with conidia spore suspension of tomato ring fungus (Alternaria solani) was carried out and kept in a humid chamber at 22 ° C to cause the disease. Seven days after the inoculation of the bacteria, the degree of disease onset was investigated according to the following criteria, and the average degree of onset of disease in triplicate in one ward is shown in Table 5.

Degree of disease 0: No disease 〃 1: The diseased area rate of each leaf of the plant is 10% or less 〃 2: The diseased area rate of each leaf of the plant is 10 to 50% 〃 3: The diseased area rate of each leaf of the plant is over 50

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A01N 43/713 9159-4H 43/76 9159-4H 43/78 D 9159-4H 43/82 101 9159 -4H 104 9159-4H 43/84 101 9159-4H 43/86 101 9159-4H 47/10 Z 9159-4H 57/22 D 9159-4H C07D 401/04 209 7602-4C 401/06 209 7602-4C 403 / 04 209 7602-4C 403/06 209 7602-4C 405/04 209 7602-4C 413/04 209 7602-4C 417/04 209 9051-4C 417/06 209 9051-4C (72) Inventor Takayuki Ueda Tokyo Sanoh Co., Ltd. 1-258 Hiromachi, Shinagawa-ku (72) Inventor Ichiro Nakanishi 1041 Yasu, Yasu-cho, Yasu-gun, Shiga In-house (56) Reference JP 60-161968 (JP, A)

Claims (2)

[Claims] 1. A compound having the following general formula: [In the formula, R ¹ and R ² are the same or different from each other and each represent a C ₁ -C ₆ alkyl group, R ³ represents a hydrogen atom, and R ⁴
Nitro group, amino group, one or two aliphatic carboxylic acyl substituents amino group having a heterocyclic group, an aliphatic carboxylic acyl group, C ₂ -C ₄ alkenyl or C _1, -
C ₄ -substituted alkyl or C ₂ -C ₄ -substituted alkenyl group is shown, which has 1 or 2 substituents and is selected from the following group: group —XR ⁵ (X is an oxygen atom, a sulfur atom or indicates -NH-, R ⁵ is a hydrogen atom, C ₃ -C ₈ cycloalkyl group, C ₂ -C ₄ alkenyl group, C ₂ -C ₄ alkynyl group, an aryl group, a carboxy group, an acyl groups, C ₁ -C ₆ alkyl group, or C ₁ -C ₆ alkyl group having at least one cyano, nitro, C ₁ -C ₄ alkoxy, aryl, aryloxy or C ₁ -C ₄ alkylamino substituent), halogen atom, heterocyclic group , Carboxy group, thiocarboxy group, cyano group, aliphatic carboxylic acid acyl group, aromatic carboxylic acid acyl group, nitro group, di (C ₁ -C ₃ alkoxy) phosphoryl group and hydroxyimino group], and R ⁴ is carboxy Group, thiocarbox When it is a group containing a silane group, their corresponding halides, esters, amides and salts thereof, or when R ⁴ is a group containing a hydroxyl group or a mercapto group, their ester, or R ⁴ is When it is a substituted or unsubstituted amino group, an acid addition salt thereof. 2. An agricultural and horticultural fungicide containing a compound having the following general formula as an active ingredient: [In the formula, R ¹ and R ² are the same or different from each other and each represent a C ₁ -C ₆ alkyl group, R ³ represents a hydrogen atom, and R ⁴
Nitro group, amino group, one or two aliphatic carboxylic acyl substituents amino group having a heterocyclic group, an aliphatic carboxylic acyl group, C ₂ -C ₄ alkenyl or C _1, -
C ₄ -substituted alkyl or C ₂ -C ₄ -substituted alkenyl group is shown, which has 1 or 2 substituents and is selected from the following group: group —XR ⁵ (X is an oxygen atom, a sulfur atom or indicates -NH-, R ⁵ is a hydrogen atom, C ₃ -C ₈ cycloalkyl group, C ₂ -C ₄ alkenyl group, C ₂ -C ₄ alkynyl group, an aryl group, a carboxy group, an acyl groups, C ₁ -C ₆ alkyl group, or C ₁ -C ₆ alkyl group having at least one cyano, nitro, C ₁ -C ₄ alkoxy, aryl, aryloxy or C ₁ -C ₄ alkylamino substituent), halogen atom, heterocyclic group , Carboxy group, thiocarboxy group, cyano group, aliphatic carboxylic acid acyl group, aromatic carboxylic acid acyl group, nitro group, di (C ₁ -C ₃ alkoxy) phosphoryl group and hydroxyimino group], and R ⁴ is carboxy Group, thiocarbox When it is a group containing a silane group, their corresponding halides, esters, amides and salts thereof, or when R ⁴ is a group containing a hydroxyl group or a mercapto group, their ester, or R ⁴ is When it is a substituted or unsubstituted amino group, an acid addition salt thereof.