JPH06321893A - Oxime ether compound, its production and antimicrobial agent - Google Patents

Abstract

PURPOSE:To obtain the subject novel compound having an excellent antimicrobial potency, substantially not exhibiting chemical toxicities and useful as an antimicrobial agent for agriculture and horticulture by reacting a specific alpha-ketoester compound with a hydroxyl amine compound. CONSTITUTION:This method for producing the oxime ether compound comprises reacting an alpha-keto ester compound of formula I (R<3> is 3-8C cycloalkyl; R<4> is 3-6C alkenyloxy, 3-6C alkinyloxy, 1-10C alkoxy, 1-6C alkylthio, 1-6C alkyl, etc.; R<5> is 1-6C alkyl; (n) is 0-5) with a hydroxylamine compound of formula II (R<1> is 1-6C alkyl) in a solvent such as methanol at room temperature for 4 hrs, filtering the reaction solution, distilling off the solvent under vacuum, adding diethyl ether to the residues, and subsequently purifying the solution with a column chromatography, thus providing the objective novel oxime ether compound of formula III [R<2> is OR<5>, NHR<6> (R<6> is 1-6C alkyl)] having an excellent antimicrobial potency and substantially not exhibiting chemical toxicities.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel oxime ether compound useful as a bactericide.

[0002]

Description of the Prior Art Oxime ether compounds which are effective as germicides include the following formulas described in JP-A-63-23852:

[0003]

[Chemical 5]

[Wherein R ¹ and R ² are the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X (m = 1 to 5) is a halogen atom, Cyano group, trifluoromethyl group, nitro group, C ₁
-C ₄ - alkyl group, C ₁ -C ₄ - alkoxy, optionally substituted phenyl, optionally substituted phenoxy group, the same or different substituents, or a hydrogen atom benzyloxy group optionally substituted with And Y represents a methyleneoxy group, an oxymethylene group, an ethylene group, an ethenylene group, an ethynylene group or an oxygen atom. In addition,
The definitions given herein for R ¹ , R ² , X, m and Y are limited to this compound only. ] And the following formulas described in JP-A-3-246268:

[0005]

[Chemical 6]

[Wherein R¹And R²Respectively water
Elemental, lower alkyl, or cyclo (lower) alkyl: R
³Is lower alkyl, or cyclo (lower) alkyl: R
^FourAnd R^FiveAre hydrogen, lower alkyl, lower
Alkoxy, halogenated lower alkyl, lower alkyl
Ryl, halogen, or nitro: A is an unsaturated hydrocarbon
Elemental, halogenated unsaturated hydrocarbons, or substitution of 3 or less
Phenyl or heterocycle optionally substituted with groups
Group: Z is -CH₂-, -CH (OH)-, -CO-,
-O-, -S-, -NR- (R is hydrogen or lower alkyl
Kill), -CH₂CH₂-, -CH = CH-, ethylene
Oxide, -CH₂O-, -CH₂S-, -CH ₂SO
-, -OCH₂-, -SCH₂-Or-SOCH₂
Represents-. In addition, R described here¹~ R^Five, Z and A
Is limited to this compound only. ]
Compounds are known. But as in the present invention
Oxime ether compounds and their synthetic intermediates are known
The oxime ether compound of the present invention has a bactericidal activity.
Not known to be superior in sex and phytotoxicity
It was

[0007]

The object of the present invention is to provide a novel oxime ether compound, a synthetic intermediate thereof, a process for producing these compounds, and a fungicide containing the novel oxime ether compound as an active ingredient. is there.

[0008]

Means for Solving the Problems As a result of studies to solve the above-mentioned problems, the present inventors have found that the novel oxime ether compound has almost no phytotoxicity and has a remarkable bactericidal activity for agriculture and horticulture. In addition, they have found that a novel compound can be used as the synthetic intermediate, and have completed the present invention. That is, the present invention is as follows. The first invention is
Formula (I):

[0009]

[Chemical 7]

[In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms; R ² represents OR ⁵ or NHR ⁶ (wherein R ⁵ and R ⁶ are different from each other; R ³ represents an alkyl group having 1 to 6 carbon atoms; R ³ represents a cycloalkyl group having 3 to 8 carbon atoms; R ⁴ represents an alkenyloxy group having 3 to 6 carbon atoms. , With 3 carbon atoms
6 alkynyloxy groups, alkoxy groups having 1 to 10 carbon atoms, benzyloxy groups, alkoxycarbonyl groups having 2 to 7 carbon atoms, halogen atoms, cyano groups, alkylthio groups having 1 to 6 carbon atoms , 1 to 6 carbon atoms
Represents an alkyl group, a haloalkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 7 carbon atoms; n is
It represents an integer of 0 to 5. ] It is related with the oxime ether type compound shown by these. In the compound (I) of the present invention, a geometrical isomer (E-form, Z
-Body) and mixtures of both are included in the present invention.
The second invention is the following formula (II):

[0011]

[Chemical 8]

(Wherein R ³ , R ⁴ , R ⁵ and n have the same meanings as described above) and the α-ketoester compound. A third invention relates to an α-ketoester compound represented by the above formula (II) and the following formula (I
II):

[0013]

[Chemical 9]

An oxime in which R ² is OR ⁵ in the above formula (I) is characterized in that a compound represented by the formula (wherein R ¹ has the same meaning as described above) is reacted. The present invention relates to a method for producing an ether compound.
A fourth invention is that R ² is OR in the above formula (I).
An oxime ether compound represented by ⁵ and the following formula (IV):

[0015]

[Chemical 10]

The oxime (wherein, R ⁶ is where is. The same as defined above described) R ² in formula (I) of the, wherein the reacting a compound represented by the represented by NHR ⁶ The present invention relates to a method for producing an ether compound.

A fifth aspect of the present invention relates to a fungicide containing the oxime ether compound represented by the above formula (I) as an active ingredient.

The present invention will be described in detail below. Previous
Novel oxime ether compound which is the target compound
(I) [compound (Ia) and compound (Ib)], which are synthetic raw materials
R in certain compounds (II) to (VI)¹, R ², R³，
R^Four, R^Five, R⁶And n are as follows.

R ¹ is, for example, 1 to 6 carbon atoms.
There may be mentioned linear or branched alkyl groups; preferably those having 1 to 4 carbon atoms;
More preferably, it is a methyl group. R ² is OR
⁵ , NHR ⁶ can be mentioned. R ⁵ in R ²
Examples of R ⁶ and R ⁶ include linear or branched alkyl groups having 1 to 6 carbon atoms which may be different from each other; preferably, those having 1 to 4 carbon atoms And more preferably a methyl group.

R ³ is, for example, 3 to 8 carbon atoms.
Cycloalkyl groups can be mentioned; preferred are those having 3 to 8 carbon atoms; and more preferred are cyclopropyl and cyclobutyl groups. R ⁴ is an alkenyloxy group having 3 to 6 carbon atoms, an alkynyloxy group having 3 to 6 carbon atoms, or 1 to 1 carbon atoms.
10 alkoxy groups, benzyloxy group, alkoxycarbonyl group having 2 to 7 carbon atoms, halogen atom, cyano group, alkylthio group having 1 to 6 carbon atoms, alkyl group having 1 to 6 carbon atoms, Examples thereof include a haloalkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 7 carbon atoms.

Examples of the alkenyloxy group having 3 to 6 carbon atoms in R ⁴ include linear or branched ones; preferably 3 carbon atoms.
Or four, and more preferably an allyloxy group. At this time, n represents an integer of 0 to 5; preferably 1 or 2, and more preferably 1.
The substitution position of R ⁴ is not particularly limited; however, it is preferably the 4-position.

Examples of the alkynyloxy group having 3 to 6 carbon atoms in R ⁴ include linear or branched ones; preferably 3 carbon atoms.
Or four, and more preferably a propargyloxy group. At this time, n represents an integer of 0 to 5; preferably 1 or 2, and more preferably 1. Further, the substitution position of R ⁴ is not particularly limited;
It is preferably the 4th place.

Examples of the alkoxy group having 1 to 10 carbon atoms in R ⁴ include linear or branched ones; preferably 1 to 4 carbon atoms.
And a methoxy group or an ethoxy group. At this time, n represents an integer of 0 to 5;
It is preferably 1 or 2. The substitution position of R ⁴ is
Although not particularly limited, it is preferably at the 3, 4, and 5 positions.

When R ⁴ is a benzyloxy group, n is 0
Represents an integer of 5; preferably 1 or 2; and more preferably 1. The substitution position of R ⁴ is not particularly limited; it is preferably the 3 and 4 positions.

Examples of the alkoxycarbonyl group having 2 to 7 carbon atoms in R ⁴ include linear or branched ones; preferably those having 2 to 5 carbon atoms. Yes; more preferably a methoxycarbonyl group. At this time, n represents an integer of 0 to 5; preferably 1 or 2, and more preferably 1
Is. The substitution position of R ⁴ is not particularly limited; however, it is preferably the 4-position.

The halogen atom for R ⁴ includes, for example, chlorine atom, iodine atom, bromine atom, fluorine atom and the like; preferably chlorine atom and fluorine atom. At this time, n represents an integer of 0 to 5;
It is preferably 1 or 2; more preferably 1. Further, the substitution position of R ⁴ is not particularly limited; however, it is preferably 2, 3, 4 position.

When R ⁴ is a cyano group, n is 0 to 5
Represents an integer; preferably 1 or 2, and more preferably 1. The substitution position of R ⁴ is not particularly limited; however, it is preferably the 4-position.

Examples of the alkylthio group having 1 to 6 carbon atoms in R ⁴ include linear or branched ones; preferably those having 1 to 4 carbon atoms; A methylthio group is preferred. At this time, n represents an integer of 0 to 5; preferably 1 or 2
And more preferably 1. The substitution position of R ⁴ is not particularly limited, but it is preferably the 3-position.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁴ include linear or branched ones; preferably those having 1 to 4 carbon atoms; Preferred are a methyl group and an ethyl group. At this time, n represents an integer of 0 to 5; preferably 1 or 2, and more preferably 1. The substitution position of R ⁴ is not particularly limited; it is preferably the 3 and 4 positions.

The haloalkyl group having 1 to 6 carbon atoms in R ⁴ has a linear or branched alkyl group (as the halogen atom, for example, those described above can be mentioned. , And a fluorine atom is preferable); preferably, those having 1 to 4 carbon atoms; and more preferably trifluoromethyl group. At this time, n represents an integer of 0 to 5; preferably 1 or 2, and more preferably 1
Is. The substitution position of R ⁴ is not particularly limited; however, it is preferably the 4-position.

Examples of the acyl group having 2 to 7 carbon atoms in R ⁴ include linear or branched ones; preferably those having 2 to 5 carbon atoms; Preferred is an acetyl group. At this time, n
Represents an integer of 0 to 5; preferably 1 or 2, and more preferably 1. Further, the substitution position of R ⁴ is not particularly limited; however, the 4-position is preferable.

Compound (Ia) [in compound (I), R ²
Is a compound represented by OR ⁵ ], R ¹ is an alkyl group having 1 to 6 carbon atoms, R ³ is a cycloalkyl group having 3 to 8 carbon atoms, and R ⁴ is 3 to 6 carbon atoms. Alkenyloxy groups, alkynyloxy groups having 3 to 6 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, benzyloxy groups, alkoxycarbonyl groups having 2 to 7 carbon atoms, halogen atoms, cyano groups , An alkylthio group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, or no R ^4. The thing of a substituent can be mentioned.

A compound (I
a) is R ¹ when R ³ is a cyclopropyl group.
Is a methyl group; R ⁴ is an allyloxy group, propargyloxy group, methoxy group, ethoxy group, benzyloxy group, methoxycarbonyl group, fluorine atom, chlorine atom, cyano group, methylthio group, methyl group, trifluoromethyl group, An acetyl group or R ⁴ is an unsubstituted group.
When R ³ is a cyclobutyl group, R ¹ is a methyl group; R ⁴ is a chlorine atom.

In view of phytotoxicity, the preferred compound (Ia) is such that R ³ is a cyclopropyl group; R ¹ is a methyl group; R ⁴ is an allyloxy group, propargyloxy group, methoxy group, fluorine Atom, chlorine atom, cyano group, methyl group, trifluoromethyl group.

Compound (Ib) [in compound (I) R ²
Is a compound represented by NHR ⁶ ], R ¹ is an alkyl group having 1 to 6 carbon atoms; R ³ is a cycloalkyl group having 3 to 8 carbon atoms; R ⁴ is 3 to 6 carbon atoms. Alkenyloxy groups, alkynyloxy groups having 3 to 6 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, benzyloxy groups, halogen atoms, cyano groups, 1 to 6 carbon atoms
Alkylthio groups, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, acyl groups having 2 to 7 carbon atoms, or those in which R ⁴ is an unsubstituted group You can

Then, a compound (I
a), when R ³ is a cyclopropyl group, R ¹ is a methyl group; R ⁴ is an allyloxy group, propargyloxy group, a methoxy group, an ethoxy group, a benzyloxy group,
Methoxycarbonyl group, fluorine atom, chlorine atom, cyano group, methylthio group, methyl group, trifluoromethyl group,
An acetyl group or R ⁴ is an unsubstituted group. R ³
Is a cyclobutyl group, R ¹ is a methyl group;
R ⁴ is a chlorine atom or a fluorine atom.

In view of phytotoxicity, the preferred compound (Ib) is R ³ is cyclopropyl group; R ¹ is methyl group; R ⁴ is allyloxy group, propargyloxy group, methoxy group, fluorine An atom, a chlorine atom, a cyano group, a methyl group, a trifluoromethyl group, or R ⁴ is an unsubstituted group.

As a preferred embodiment for producing the oxime ether compound represented by the above-mentioned formula (I), in addition to the synthesis method 1 of the third invention and the synthesis method 2 of the fourth invention, The synthetic method 3 shown can be mentioned. [Synthesis Method 3] Formula (V):

[0039]

[Chemical 11]

(Wherein R ¹ and R ⁵ have the same meanings as described above; X represents a leaving group) and the following formula (VI):

[0041]

[Chemical 12]

(In the formula, R ³ , R ⁴ and n have the same meanings as described above.) In the above-mentioned formula (I), R ² is OR. ^Five
A method for producing an oxime ether compound represented by. The synthetic methods 1 to 3 of the compound (I) of the present invention will be described in more detail. (Synthesis Method 1) Compound (Ia) [a compound (I) wherein R ² is represented by OR ⁵ ] is synthesized by reacting compound (II) with compound (III) in a solvent. You can

[0043]

[Chemical 13]

(Wherein R ¹ , R ³ , R ⁴ , R ⁵ and n
Is as defined above. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), alcohols (methanol, ethanol, n-propanol, i.
-Propanol, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.),
Examples thereof include water and a mixture of the aforementioned solvents; preferably, a mixture of alcohols and water is preferable. The amount of the solvent used is such that the concentration of the compound (Ia) is 0.5 to
It can be used in a concentration range of 80% by weight, but it is preferable to use the compound (Ia) in a concentration of 1 to 50% by weight.

The reaction temperature is not particularly limited, but it is -30.
Within the temperature range from ℃ to the boiling point of the solvent used, 0
-50 degreeC is preferable. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 0.5 to 30 hours. The amount of the raw material compound used is 1 to 50 times mol of the compound (III) with respect to the compound (II), but preferably 1
It is preferably about 5 times by mole. Compound (II) is, for example,
It can be manufactured by carrying out as shown in the following formula.

[0046]

[Chemical 14]

(Wherein R ³ , R ⁴ , R ⁵ , n and X are
It is synonymous with the above description. ) Compound (VI) and compound (VII) are mixed in an amount of 0.1 to 3 times mol (preferably 0.5 to 1.5 times mol) in an organic solvent that does not affect the reaction (for example, the number of carbon atoms). 1-10 ketones, tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, dioxane) are added and dissolved, and a base (for example, an alkali metal alcoside having 1 to 5 carbon atoms, an alkali metal carbonate, an alkali metal) is used. 0 to 150 ° C. (preferably 30 to 80) in the presence of hydroxide.
0.5 to 12 hours (preferably 0.5 to 3 hours)
It can be obtained by stirring. As X,
Examples thereof include leaving groups such as p-toluenesulfonyloxy, methanesulfonyloxy, and a halogen atom; preferably a halogen atom; and more preferably a bromine atom.

The compound (II) is, for example, a compound (II) consisting of the kinds of substituents corresponding to the compounds (Ia-1) to (Ia-21) shown in Tables 1 to 3 below. [Compounds (II) _Ia-1 to (II) _Ia-21 . For example, the compound (II) _Ia-1 is represented by R ^{3 in the} formula represented by the compound (II).
Is a cyclopropyl group, R ⁵ is a methyl group, (R ⁴ ) _n is p
An allyloxy group. ] Can be mentioned. As the compound (III), a commercially available product [o-methylhydroxylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd., product number M0343)] can be used.

Since the compound (III) used in the synthesis of the compound (Ia) of the present invention has an amino group, these acid addition salts can be used instead of them. Examples of acids that form acid addition salts include inorganic acids (hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, etc.), carboxylic acids (formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid,
Examples thereof include oleic acid, aconitic acid, etc., organic sulfonic acids (methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), saccharin and the like. The target compound (Ia) produced as described above is
After completion of the reaction, usual post-treatments such as extraction, concentration and filtration are carried out, and if necessary, it can be appropriately purified by a known means such as recrystallization and various chromatography.

Examples of the compound (Ia) include compounds (Ia-1) to (Ia-21) shown in Tables 1 to 3 described later [Compound (Ia-1) is a compound In the formula (I), R ¹ and R ⁵ are methyl groups, R ³ is a cyclopropyl group, and (R ⁴ ) n is a p-allyloxy group. ].

(Synthesis Method 2) Synthesis of compound (Ib) [compound (I) wherein R ² is NHR ⁶ ] is
It can be carried out by reacting compound (Ia) with compound (IV) in a solvent or without solvent.

[0052]

[Chemical 15]

(In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and n have the same meanings as described above.) As the solvent, for example, ethers described in Synthesis Method 1,
In addition to alcohols, amides, water, etc., chlorinated or unaromaticized aromatic, aliphatic, alicyclic hydrocarbons, nitriles (acetonitrile, propionitrile, etc.), organic bases (triethylamine, Pyridine, N, N
-Dimethylaniline), 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, a mixture of the above-mentioned solvents, and the like.

The amount of the solvent used is the compound (Ia)
The compound (Ia) may be used in a concentration range of 1 to 80% by weight, but it is preferable to use the compound (Ia) in a concentration of 1 to 50% by weight. The reaction temperature is not particularly limited, but is within a temperature range of -30 ° C to the boiling point of the solvent used, and preferably 0 to 80 ° C. The reaction time varies depending on the above-mentioned concentration and temperature, but can be usually 1 to 30 hours.

The amount of the raw material compound used is 1 to 50 times mol, preferably 1 to 5 times mol of compound (IV) with respect to compound (Ia). As the compound (IV), a commercially available product [methylamine methanol solution 40% (manufactured by Wako Pure Chemical Industries, Ltd., product number 131-10395)] can be used. Compound (Ib) used in the synthesis of compound (Ib) of the present invention
Since V) has an amino group, these acid addition salts can also be used instead of them. The desired compound (Ib) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after completion of the reaction, and if necessary, known means such as recrystallization and various chromatographies. It can be appropriately purified.

Examples of the compound (Ib) include those shown in Table 4 below.
To compound (Ib-1) to compound (Ib-21) shown in [6] [Compound (Ia-1) is a compound represented by the formula (I) in which R ¹ and R ⁶ are methyl groups. , R ³ is a cyclopropyl group, and (R ⁴ ) is a p-allyloxy group. ].

(Synthesis Method 3) As shown below, the compound (Ia) can be synthesized by reacting the compound (V) with the compound (VI) in a solvent or without a solvent.
In order to accelerate the reaction, it is preferable to react in the presence of a base.

[0058]

[Chemical 16]

(In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , n and X have the same meanings as described above.) As the solvent, in addition to those described in Synthesis Method 2, ketones (acetone) , Methyl ethyl ketone, etc.). The amount of the solvent used may be such that the concentration of the compound (V) is in the concentration range of 1 to 80% by weight, but the concentration of the compound (V) is preferably 1 to 50% by weight. It is good to use it as.

The base is not particularly limited and includes, for example,
Organic bases (eg triethylamine, pyridine, N,
N-dimethylaniline, DBU, etc.), alkali metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium-t-butoxide, etc.), inorganic bases (eg, sodium hydride, sodium amide,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium hydrogen carbonate, potassium carbonate, etc.); but alkali metal alkoxides are preferred.

The amount of the base used can be 0.5 to 10 times by mole with respect to the compound (V), but preferably 0.8 to 5 times by mole.
The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent used or less, and preferably 30 to 110 ° C. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 0.3 to 30 hours. The amount of the raw material compound used is the compound (VI) relative to the compound (V).
Is 0.5 to 2 times, but preferably 0.8 to 1.
It is preferably 5 times the molar amount. Compound (V) used in the present invention
For example, as shown below, compound (VII) and compound (I
It can be produced by reacting II) with a solvent.

[0062]

[Chemical 17]

(In the formula, R ¹ , R ⁵ and X have the same meanings as described above.) As the solvent, ethers, alcohols, amides, water and synthetic method 2 described in the synthetic method 1 can be used. The hydrocarbons, nitrites, organic bases, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, mixtures of the above-mentioned solvents and the like can be mentioned. The solvent can be used such that the concentration of the compound (V) is in the concentration range of 1 to 80% by weight. The reaction temperature is not particularly limited, but it can be carried out within a temperature range from room temperature to the boiling point of the solvent used or less. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 2 to 30 hours.

The amounts of these compounds used are the same as those of compound (VII)
Compound (III) is 0.5 to 3 times by mole, preferably 0.5 to 1.7 times by mole. After completion of the reaction, the compound (V) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration, and optionally purified by a known means such as recrystallization and various chromatography. can do.

Examples of the compound (V) include compounds (Va) consisting of the kinds of substituents corresponding to the compounds (Ia-1) to (Ia-21) shown in Tables 1 to 3 below. [Compounds (V) _Ia-1 to (V) _Ia-21 are referred to. In addition, this compound (V) includes a geometrical isomer (E-
Body, Z-body) and mixtures of both. For example, in the compound (V) _Ia-1 , R ¹ and R ⁵ in the formula represented by the compound (V) are methyl groups, X is a halogen atom, and the oxime ether moiety is in the E configuration. ] Can be mentioned. Compound (VI) can be prepared, for example, according to J. Vos as shown in the following formula.
s, W. Walter, Ann. 716 , 209 (1986).

[0066]

[Chemical 18]

(In the formula, R ³ , R ⁴ and n have the same meanings as described above.) Examples of the compound (VI) include compounds (Ia-1) shown in Tables 1 to 3 below. ~ Compound (VI) [Compound (VI) _Ia-1 ~ consisting of the type of each substituent corresponding to compound (Ia-21), etc.
(VI) _{Referred to as Ia-21} . For example, compound (VI) _Ia-1 is
In the formula represented by the compound (VI), R ³ is a cyclopropyl group and (R ⁴ ) _n is a p-allyloxy group. ] Can be mentioned.

Examples of the compound (Ia) include compounds (Ia-1) to (Ia-21) shown in Tables 1 to 3 described later [Compound (Ia-1) is a compound In the formula (I), R ¹ and R ⁵ are methyl groups, R ³ is a cyclopropyl group, and (R ⁴ ) n is a p-allyloxy group. ].

Examples of agricultural and horticultural pathogens which have a controlling effect with the compound (I) of the present invention include, for example, wheat leaf rust,
Examples include barley powdery mildew, cucumber downy mildew, rice blast, and tomato plague.

The bactericide of the present invention shows almost no phytotoxicity against agricultural and horticultural crops such as cucumber, and has a remarkable bactericidal effect, and contains at least one compound (I) as an active ingredient. It is contained as. The compound (I) can be used alone, but it is usually a carrier,
Use by blending surfactants, dispersants, auxiliaries, etc. (prepared as a composition such as powder, emulsion, fine granules, granules, wettable powder, oily suspension, aerosol) preferable.

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbonization. Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Examples of surfactants and dispersants that can be used to improve the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. In order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in suitable combination according to the purpose.
The concentration of the active ingredient when the compound (I) of the present invention is formulated is usually 1 to 50% by weight in the case of emulsion and 0.3 in the case of powder.
25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oils, usually 0.1 to 5% by weight for aerosols. is there. These formulations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, water surface of paddy field or directly applied to various applications depending on the purpose.

[0074]

EXAMPLES The present invention will be specifically described below with reference to examples and examples. It should be noted that these examples do not limit the scope of the present invention. Reference Example 1 [Synthesis of compound (V)] (1) Synthesis of methyl 2- (2'-bromomethylphenyl) -2-methoxyiminoacetate Methyl 2- (2'-bromomethylphenyl) -2-oxoacetate ( 27.7 g) was dissolved in methanol (200 ml), water (1.0 ml) was added, and then o-methylhydroxylamine hydrochloride (9.10 g) was added and dissolved while stirring. After stirring overnight at room temperature, the solvent was distilled off under reduced pressure. Ethyl acetate (400 m
l) was added and washed three times with saturated saline (200 ml),
It was dried over anhydrous magnesium sulfate. After drying, it was filtered and the filtrate was concentrated under reduced pressure to give a brown oily residue. The obtained residue is subjected to column chromatography [Wako Gel C-20
0, (toluene: ethyl acetate) is eluted from (50: 1) to (9: 1)], and 10 g of the target product (E isomer), which is a pale yellow oily liquid, is first eluted, and then As a result, 10 g of the desired product (Z isomer), which was a pale yellow oily liquid, was eluted.

(Physical properties of isomers) E isomer ¹ H-NMR (270 MHz, 297 K, CDCl ₃ ,
TMS) δ: 7.60 to 7.00 (4H, m), 4.3
4 (2H, s), 4.07 (3H, s), 3.89 (3
H, s) ppm

Z isomer ¹ H-NMR (270 MHz, 297 K, CDCl ₃ ,
TMS) δ: 7.60 to 7.00 (4H, m), 4.4
4 (2H, s), 4.06 (3H, s), 3.87 (3
H, s) ppm

Example 1 (A) [Synthesis of Compound (II)] (1) Methyl 2- {cyclopropyl- (4'-ethoxyphenylimino) methylthiomethyl} phenyloxoacetate [Compound (II) _Ia-1 ] Synthesis of 2- (2′-bromomethylphenyl) -2-oxoacetate methyl (5.0 g) in tetrahydrofuran (100 m
l) was added, cyclopropylcarbothio-4′-ethoxyanilide (4.3 g) was dissolved, potassium-tert-butoxide (2.6 g) was added with stirring, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and the solvent was distilled off under reduced pressure. Diethyl ether (20
0 ml) was added, and the mixture was washed with saturated saline (100 ml) three times, and the ether layer was dried over anhydrous magnesium sulfate. After drying, it was filtered and the filtrate was concentrated under reduced pressure to give a brown oily residue. The obtained residue was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 4: 1) to obtain 1.2 g of the target substance, which was a first pale yellow oily liquid.

(Physical properties) ¹ H-NMR (400 MHz, 297 K, CDCl ₃ ,
TMS) delta: 7.75 to 7.25 (4H, m), 7.0.
0 to 6.65 (4H, m), 4.56 (2H, s),
4.02 (2H, q, 8.0Hz), 3.94 (3H,
s), 1.85 to 1.68 (1H, m), 1.43 (3
H, t, 8 Hz), 1.10 to 0.65 (4H, m) p
pm

(2) Other compounds (II) corresponding to the compounds (I) in Tables 1 to 3 below were synthesized by the same method as described above. (B) [Synthesis of Compound (I)] (1) 2- [2 '-{cyclopropyl- (4 "-ethoxyphenylimino) methylthiomethyl} phenyl] -2-
Methyl methoxyiminoacetate [Compound (Ia-3a) and compounds
Synthesis of (Ia-3b)] 2- {cyclopropyl- (4′-ethoxyphenylimino) methylthiomethyl} phenyloxoacetate (0.9 g) was dissolved in methanol (50 ml), and then potassium carbonate (3 0.1 g) was added and stirred. O-Methylhydroxylamine hydrochloride (0.2g)
Was added and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the mixture was left standing overnight and filtered, then the solvent was distilled off under reduced pressure, diethyl ether (50 ml) was added to the residue, and saturated saline solution (50 m) was added.
Washed 3 times with l). After the ether layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography (Wako Gel C-200,
By purification with toluene: ethyl acetate = 4: 1 (elution), 0.6 g of the oily target product was obtained.

(2) E-2- [2 '-{cyclopropyl-
Synthesis of methyl (3 ", 5" -dimethoxyphenylimino) methylthiomethyl} phenyl] -2-methoxyiminoacetate [Compound (Ia-6a)] Cyclopropylcarbothio-3 ', 5'-dimethoxyanilide (1.0 g ) To tetrahydrofuran (50 ml)
After being dissolved in water, methyl E-2- (2′-bromomethylphenyl) -2-methoxyiminoacetate (1.2 g) was added, and potassium-tert-butoxide (0.77) was added with stirring.
g) was added and the mixture was heated under reflux for 3 hours. The reaction mixture was concentrated under reduced pressure and diethyl ether (100 ml) was added to the residue.
Was added, and the mixture was washed 3 times with saturated saline (50 ml). The ether layer was dried over anhydrous magnesium sulfate, filtered, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography [Wakogel C-200, (toluene: ethyl acetate) (9: 1). By elution until (4: 1)], 0.62 g of the oily target product was obtained.

(3) 2- [2 '-{cyclopropyl-
(4 "-tolylimino) methylthiomethyl} phenyl]
Synthesis of methyl 2-methoxyiminoacetate [Compound (Ia-15)] Cyclopropylcarbothio-4′-methylanilide (0.76 g) was dissolved in tetrahydrofuran (50 ml), and then E-2- (2′- Bromomethylphenyl)-
Methyl 2-methoxyiminoacetate (1.14 g) was added,
Potassium-tert-butoxide (0.54 g) with stirring
After adding, the mixture was heated under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, diethyl ether (100 ml) was added to the residue, and the mixture was washed 3 times with saturated brine (50 ml). The ether layer was dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 9: 1). , 1.05 g of an oily target product was obtained.

(4) N-methyl-2- [2 '-{cyclopropyl- (3 ", 5" -dimethoxyphenylimino) methylthiomethyl} phenyl] -2-methoxyiminoacetic acid amide [compound (Ib-6)] ] 2- [2 '-{cyclopropyl- (3 ", 5" -dimethoxyphenylimino) methylthiomethyl} phenyl]-
Methyl 2-methoxyiminoacetate (0.62 g) was dissolved in methanol (20 ml), 40% methylamine methanol solution (1.08 g) was added, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure and the resulting residue was purified by column chromatography [Wakogel C-200, (toluene: ethyl acetate) eluted from (9: 1) to (4: 1)]. 0.4 g of oily target product
Obtained.

(5) N-methyl-2- [2 '-{cyclopropyl- (4 "-tolylimino) methylthiomethyl} phenyl] -2-methoxyiminoacetic acid amide [Compound (Ib-
13)] Synthesis of 2- [2 ′-{cyclopropyl- (4 ″ -tolylimino) methylthiomethyl} phenyl] -2-methoxyiminoacetate (0.75 g) in methanol (20 ml)
40% methylamine methanol solution (1.50 g) was added, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to obtain 0.5 g of the oily desired product.

(6) Other compounds (I) in Tables 1 to 6 were synthesized according to the above method. The compounds and their physical properties are shown in Tables 1 to 11.

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

[Table 6]

[0091]

[Table 7]

[0092]

[Table 8]

[0093]

[Table 9]

[0094]

[Table 10]

[0095]

[Table 11]

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound (Ia-1), 35 parts by weight of bentonite, 57 parts by weight of talc, neoperex powder (trade name; manufactured by Kao Corporation) ) 1 part by weight and 2 parts by weight of sodium lignin sulfonate were uniformly mixed, a small amount of water was added and kneaded, and then granulated and dried to obtain a granule.

(2) Preparation of wettable powder: 10 parts by weight of compound (Ia-1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation). And 0.5 part by weight of DEMOL (trade name; manufactured by Kao Corporation) were uniformly mixed and then pulverized to obtain a wettable powder.

(3) Preparation of emulsion 20 parts by weight of compound (Ia-1) and 70 parts by weight of xylene were added,
10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) was added and uniformly mixed and dissolved to obtain an emulsion.

(4) Preparation of Dust Preparation A compound (Ia-1) (5 parts by weight), talc (50 parts by weight) and kaolin (45 parts by weight) were uniformly mixed to obtain a powdery product.

Example 3 [Efficacy test] (1) Control efficacy test against cucumber downy mildew One cucumber (cultivar; Sagamihanjiro) is grown in a plastic flower pot with a diameter of 6 cm, and 1.5 leaf stage Of the target compound (I) shown in Tables 1 to 6 in accordance with Example 2 was added to the seedlings of
%) And diluted to a predetermined concentration (200 or 500 ppm) and sprayed at 20 ml per pot. After spraying, 2
After cultivating in a glass greenhouse for one day, zoospores of cucumber downy mildew (Pseudoperonospora cubensis) were prepared from diseased leaves, which were uniformly spray-inoculated on the back surface of plant leaves. After inoculation, the mixture was kept in the dark at 20 ° C. for 2 days and then grown in a glass greenhouse for 5 days to examine the degree of cucumber downy mildew lesions appearing on the first leaf.

Evaluation of the drug effect was carried out in 6 levels (0: whole diseased, 1: lesion area was about 60%, 2: lesion area was about 40%, in comparison with the degree of lesions in the untreated section. 3: The lesion area is about 20%, 4: The lesion area is 10% or less, and 5: No lesion). In addition, as a comparative example, JP-A-63-2
The following formula (A) of compound number 100 described in Japanese Patent No. 3852;

[0102]

[Chemical 19]

Comparative compound A represented by: and JP-A-3-24
No. 6268, the following formula (B) of Compound No. 3;

[0104]

[Chemical 20]

Comparative compound B represented by was examined in the same manner as in the case of compound (I). The results are shown in Table 12.

[0106]

[Table 12]

(2) Control efficacy test against rice blast (preventive effect) Ten rice (cultivar; Nihonbare) was grown in a plastic flower pot with a diameter of 6 cm, and seedlings at 1.5 leaf stage were grown. Each wettable powder of the compound (I) shown in Tables 1 to 6 prepared according to Example 2 was diluted to a predetermined concentration (200 or 500 ppm) with water containing a surfactant (0.01%). ,
20 ml was sprayed per pot. After spraying, it was cultivated in a glass greenhouse for 2 days, and then a conidial suspension of rice blast fungus prepared from diseased leaves was uniformly spray-inoculated onto plant leaves. After inoculation, it was grown in a humid chamber at 28 ° C. for 5 days, and the degree of rice blast lesions appearing on the leaves was examined. The result is
Table 13 shows the six-level evaluation method of (1).

[0108]

[Table 13]

(3) Control efficacy test against barley powdery mildew (preventive effect) 10 barleys (cultivar: black wheat) were grown in a plastic flower pot with a diameter of 6 cm, and 1.5 leaf stage seedlings were grown. In addition, each wettable powder of the compound (I) shown in Tables 1 to 6 prepared according to Example 2 was mixed with a surfactant (0.01%).
Each of them was diluted to a predetermined concentration (200 or 500 ppm) with water containing 20 ml and sprayed with 20 ml of each chemical solution. These were cultivated in a glass greenhouse for 2 days, and then the barley powdery mildew fungus sporulated spores were collected from the diseased leaves,
This was sprinkled evenly over each plant and inoculated. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew lesions appearing on each first leaf was investigated. The results are shown in Table 14 by the 6-step evaluation method described in (1) above.

[0110]

[Table 14]

(5) Control Efficacy Test Against Wheat Leaf Rust (Preventive Effect) Ten wheats (cultivar: Kobushi-komugi) were cultivated in a plastic flower pot with a diameter of 6 cm, and 10 seeds were cultivated at 1.5 leaf stage. A wettable powder of the compound (I) shown in Tables 1 to 6 prepared according to Example 2 was mixed with a surfactant (0.01
%) And diluted to a predetermined concentration (200 or 500 ppm) and sprayed at 20 ml per pot. After spraying, 2
The plants were cultivated in a glass greenhouse for one day, and then the plants were uniformly spray-inoculated with a spore suspension of wheat rust (7 × 10 ⁴ spores / ml). After inoculation, grow for 1 week in a glass greenhouse,
The degree of wheat leaf rust lesions on the first leaf was investigated.
The results are shown in Table 15 by the 6-step evaluation method described in (1) above.

[0112]

[Table 15]

Example 4 [Chemical damage test] (1) Chemical damage test for cucumber One cucumber (cultivar; Sagamihanjiro) was grown in a plastic flower pot having a diameter of 6 cm, and a 1.5-leaf stage seedling was grown. In addition, a wettable powder prepared according to Example 2 from the target compound (I) shown in Tables 1 to 6 was added with a surfactant (0.01
%) And dilute to 500 ppm with water containing 2% per pot.
Sprayed with 0 ml. After spraying, it was grown in a glass greenhouse for 5 days to evaluate the degree of chemical damage. Evaluation of phytotoxicity has four levels (+
+: Severe phytotoxicity, +: Mild phytotoxicity, ±:
The degree of phytotoxicity is extremely low,-: no phytotoxicity is observed). As comparative examples, comparative compounds A and B described in (1) of Example 3 were examined in the same manner as in the case of compound (I). The results are shown in Table 16.

[0114]

[Table 16]

[0115]

INDUSTRIAL APPLICABILITY The novel oxime ether compound of the present invention is an excellent fungicide for agricultural and horticultural use because it has almost no phytotoxicity against agricultural and horticultural crops and has an excellent bactericidal effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideaki Umeyama 5 1978, Kozugushi, Ube, Yamaguchi Prefecture 5 1978, Ube Research Co., Ltd. Ube Laboratory (72) Inventor Tadashi Murakami 5 Ube Kosan, 1978, Kobugushi, Ube City, Yamaguchi Prefecture Ube Institute Co., Ltd.

Claims (5)

[Claims] 1. The following formula (I): [In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms; R ² represents OR ⁵ or NHR ⁶ (note that R ⁵
And R ⁶ represent an alkyl group having 1 to 6 carbon atoms which may be different from each other. ); R ³ represents a cycloalkyl group having 3 to 8 carbon atoms; R ⁴ is 3-6 carbon atoms
Alkenyloxy groups, alkynyloxy groups having 3 to 6 carbon atoms, alkoxy groups having 1 to 10 carbon atoms,
Benzyloxy group, C2-C7 alkoxycarbonyl group, halogen atom, cyano group, C1-C1
Represents an alkyl group having 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 7 carbon atoms; n is an integer of 0 to 5 Represents ] The oxime ether type compound shown by these. 2. The following formula (II): ^{(Wherein, R 3, R 4, R} 5 and n are as defined in claim 1.) Alpha-keto ester compound represented by the. 3. An α-represented by the formula (II) according to claim 2.
Ketoester compounds and the following formula (III): (Wherein R ¹ has the same meaning as described in claim 1) and the compound represented by the formula (1) is reacted.
A method for producing an oxime ether compound represented by formula (I), wherein R ² is OR ⁵ . 4. The oxime ether compound of claim 3 and the following formula (IV): (Wherein R ⁶ has the same meaning as described in claim 1.) and the compound represented by the formula (1) is reacted.
A method for producing an oxime ether compound, wherein R ² is NHR ⁶ in the above formula (I). 5. A bactericide containing the oxime ether compound represented by formula (I) according to claim 1 as an active ingredient.