JP2000026214A - Industrial fungicides - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial microbicide capable of exerting its effect in lower concentration and reduced in the problems of e.g. pollution or safety by including a ketene-acetal (salt) as an active ingredient. SOLUTION: This industrial microbicide is obtained by including a ketene S,S-acetal (salt) of the formula [R1 and R2 and each e.g. H, a (halo) 1-6C alkyl, 3-6C cycloalkyl, 2-6C alkenyl or 1,3-dioxofuran-2-yl 1-6C alkyl; R1 and R2 combinedly form -(CH2)1-4 or -CH(R3)-CH2-(R3 is e.g. H, an 1-6C alkyl or methylene); and X is carbon or nitrogen] as an active ingredient. The microbicide is pref. used as an antiseptic for wood, wherein the active ingredient is pref. used in the ratio of 0.001 to 20%, more pref., 0.05 to 10% relative to the wood in concern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an industrial fungicide containing a ketene-S, S-acetal derivative or a salt thereof as an active ingredient, and more particularly to a wood preservative.

[0002]

BACKGROUND ART An imidazole derivative having a ketene dithioacetal structure is disclosed in Japanese Patent Publication No. 1-224152 as a fungicide for agriculture, and as an antifungal agent in Japanese Patent Publication No. 3-24448, JP-A-2-275877 and JP-A No. 9-245877. -10
No. 0797 describes that the optically active substance is useful as an antifungal agent, and Japanese Patent Publication No. 4-68308 discloses that a triazole derivative having a ketene dithioacetal structure is useful as an agricultural and horticultural fungicide. Has been described.

[0003]

Generally, many woods are used as interior materials in buildings and used as structural materials in wooden buildings. Wood used as interior or structural material suffers from decay, and can sometimes cause significant losses. In order to prevent such wood decay, various wood preservatives have been conventionally developed and put to practical use. As an active ingredient of these wood preservatives, there are, for example, an organic tin compound, a water-soluble chromium-copper-arsenic compound (CCA), a metal salt of naphthenic acid and the like as an inorganic or organic metal salt.
In each case, their use has been reduced due to environmental pollution problems, handling safety problems or effects.
Also, organic compounds such as chlornaphthalenes, phenols, iodopropargyl compounds and the like similarly exhibit effects at lower concentrations due to problems of pollution, safety, effects, etc., and replacement with safe compounds is required. It is becoming.

[0004]

The present invention provides a compound of the general formula (I)

Embedded image[Wherein, R¹ And R^TwoMay be the same or different, and hydrogen
Atom, C₁-C₆Alkyl group, halo C₁-C₆Alkyl group, C_Three-C
₆Cycloalkyl group, C_Two-C₆Alkenyl group, C_Two-C₆Al
Quinyl group, cyano C₁-C₆Alkyl group, C₁-C₆Alkoxy
C₁-C₆Alkyl group, C₁-C₆Alkoxy C₁-C₆Alkoxy
C₁-C₆Alkyl group, phenyl C₁-C₆Alkyl group, same or
Has one or more halogen atoms on the ring which may be different
Phenyl C₁-C₆Alkyl group or 1,3-dioxolane-
2-Il C₁-C₆Represents an alkyl group;¹ And R^TwoIs together
Become-(CH_Two)_1-4-Or-CH (R^Three) -CH_Two-(Where R^ThreeIs hydrogen
Atom, C₁-C₆Alkyl group, halo C₁-C₆Alkyl group, C₁-C
₆Alkoxy group, halo C₁-C ₆Alkoxy group, C₁-C₆Al
Kirthio group, halo C₁-C₆Alkylthio group, cyano C₁-C₆
Alkyl group, cyclo C_Three-C₆Alkyl group, methylene group, C₁
-C₆Alkoxy C₁-C ₆Alkyl group, C₁-C₆Alkylthio
C₁-C₆Alkyl group, C_Two-C₆ Alkenylcarbonyloxy
C₁-C₆Alkyl group, phenyl group, same or different
, Halogen atom, C₁-C₆Alkyl group, halo C₁-C₆Al
Kill group, C₁-C₆Alkoxy group, halo C₁-C₆Alkoxy
Group, C₁-C₆Alkylthio group, halo C₁-C₆Alkylthio group
Or C₁-C _ThreeOne or more selected from alkylenedioxy groups
A substituted phenyl group having a substituent of

A phenyl C ₁ -C ₆ alkyl group, which may be the same or different, is a halogen atom, a C ₁ -C ₆ alkyl group, a halo C ₁
-C ₆ alkyl group, C ₁ -C ₆ alkoxy group, halo C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, halo C ₁ -C ₆ alkylthio group or C ₁ -C ₃ alkylenedioxy group A substituted phenyl C ₁ -C ₆ alkyl group having at least one selected substituent on the ring, a pyridyl group, which may be the same or different, a halogen atom, a C ₁ -C ₆ alkyl group, a halo C ₁ -C ₆ Alkyl group, C ₁
A substituted pyridyl group, a naphthyl group or the same having at least one substituent selected from a -C ₆ alkoxy group, a halo C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ alkylthio group or a halo C ₁ -C ₆ alkylthio group Or may be different, a halogen atom, C ₁ -C _{6
1 selected from} an alkyl group, a halo C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a halo C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ alkylthio group and a halo C ₁ -C ₆ alkylthio group A substituted naphthyl group having the above substituent is shown. ) And X represents a carbon atom or a nitrogen atom. Ketene S, S
-An industrial bactericide containing an acetal or a salt thereof as an active ingredient.

The compound of the general formula (I) which is an active ingredient compound of the present invention
Ketene S, S-acetals represented by the formula have geometric isomers and optical isomers having an asymmetric carbon atom due to their chemical structures. Among geometric isomers, E-form, Z-form and E- and Z-form Is contained in an arbitrary ratio, and R isomers and S
And racemic forms containing the R-form and the S-form in any proportions, and among these, the R-form of the optical isomer is a preferred compound.

The compound of the general formula (I) which is an active ingredient compound of the present invention
Representative examples of ketene S, S-acetals represented by
Although shown in Table and Table 2, the present invention is not limited to these. Also, ketene S, S- represented by the general formula (I)
Acetals can be produced by a known production method described in the prior art. In Tables 1 and 2, Ph
Represents a phenyl group, c- represents an alicyclic hydrocarbon, and Q represents 1,3.
-Dioxolan-2-yl group. General formula (I-1)

Embedded image

[0008]

[Table 1]

[0009]

[Table 2]

General formula (I-2)

Embedded image

[Table 3]

[0011]

[Table 4]

[0012]

[Table 5]

[0013]

[Table 6]

[0014]

[Table 7]

[0015]

[Table 8]

[0016]

[Table 9]

In Tables 1 and 2, the NMR data of the compounds whose physical properties are viscous oils are shown in Table 3.

[Table 10]

[0018]

[Table 11]

[0019]

[Table 12]

When used as the industrial fungicide of the present invention, particularly as a wood preservative, the compounding ratio of the active ingredient varies depending on the type and generation status of the microorganism to be controlled, the number of microorganisms, and the place of habitat. The optimum throughput for use is 0.001 of active ingredient to the material to be protected.
-20%, preferably 0.05-10%. In carrying out the present invention, in order to efficiently exhibit the wood preservative effect, the ketene S, S-acetal derivative represented by the general formula (I) of the present invention is used alone or, if necessary, with other sterilizing agents. Agents, insecticides, termicides, etc., which can be mixed with oils, emulsions, solutions, suspensions,
EW agent (Emulsion in Water), ME
It can be used by formulating into general dosage forms such as preparations (Micro Emulsion), powders, granules, wettable powders, wettable powders and pastes.

The wood preservative of the present invention is applied to unused wood in the form of an emulsion, oil, liquid, EW, ME, suspension and wettable powder by applying, spraying or dipping. It can be used by methods such as pressure injection method, diffusion method, etc. It is applied to wood used for building structural materials and interior materials by application method, spraying method, foam spraying method etc. Just do it. In addition, when targeting under the floor of a house, a dusting agent or a wettable powder form of the pesticide is sprayed on the floor as it is, or a dusting agent, a granule, a suspending agent, or a wettable powder form of a pesticide is applied to a soil or the like. And spread evenly under the floor, or emulsion, suspension,
It is preferable to spray or foam a dilute solution of a wettable powder-type control agent on the soil under the floor, but the present invention is not limited to these, and the wood preservative of the present invention can effectively serve the purpose. Any form that can be exerted may be used.

The industrial bactericide of the present invention, in particular, a wood preservative, may be formulated together with an active ingredient, a surfactant, an inert carrier and, if necessary, other auxiliaries into a suitable dosage form for processing. As the inert carrier, solid carriers include, for example, clays (for example, kaolin, bentonite, pyrophyllite, acid clay, etc.) and talcs (for example, talc,
And inorganic mineral powders such as pumice and sand. These carriers may be used alone or in combination of two or more. Can be used. Examples of the liquid carrier include glycols (eg, ethylene glycol and propylene glycol), glycol ethers (eg, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol mono (2-ethylhexyl) ether), and amides (For example, N-methyl-2-pyrrolidone, N-octyl-
2-pyrrolidone), ketones (γ-butyrolactone),
Ethers (dibenzyl ether), aromatic hydrocarbons (eg, ethylbenzene, diisopropylnaphthalene,
Phenylxylylethane), aliphatic hydrocarbons (eg, white kerosene, n-paraffin), water and the like, but are not limited thereto, and these carriers may be used alone or in combination of two or more. Can be used.

The surfactants usable in the present invention include, for example, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monolaurate, alkyl allyl sorbitan monolaurate, alkyl benzene sulfonate, alkyl naphthalene sulfonate,
Examples thereof include lignin sulfonate and higher alcohol sulfate, and these surfactants can be used alone or in the form of a mixture of two or more. Further, if necessary, for the purpose of stabilizing the preparation and enhancing the efficacy, an ultraviolet absorber, an antioxidant, and a fixing agent (for example, acrylic, vinyl, polyester, polyurethane, alkyd,
Phenol, hydrocarbons, etc.).

[0024]

The present invention will be described in more detail with reference to the following Examples and Test Examples, which by no means limit the present invention. In Examples, “parts” means “parts by weight”. Example 1 Compounds described in Table 1 or 2 1 part Butyl carbitol 20 parts Naphthene solvent 79 parts The above are uniformly mixed and dissolved to prepare an oil. Example 2 Compound described in Table 1 or 2 10 parts Mixture of polyoxyethylene alkylphenol derivative and alkylaryl sulfonate 22.5 parts Dimethylformamide 22.5 parts Xylol 45 parts Emulsion obtained by uniformly mixing and dissolving the above. And

Example 3 Compounds described in Table 1 or 2 10 parts Dioctyl sulfosuccinate sodium salt 1 part Polyoxyethylene styryl phenyl ether 4 parts Ethylene glycol 5 parts Preservative 0.1 part Defoamer 1 part Increase 0.2 parts of viscous agent 78.7 parts of water The compounds described in Table 1 or 2 are wet-pulverized with water and a small amount of an activator, defoamer, thickener, etc., and then a predetermined amount of components are homogenized. To make a suspension. Example 4 Compounds described in Table 1 or 2 5 parts Dipropylnaphthalene 10 parts Mixture of polyoxyethylene styrylphenyl ether and calcium dodecylbenzenesulfonate 20 parts Diethylene glycol monobutyl ether 20 parts Water 45 parts Water is added to a mixture of the compounds shown in Table 2, a solvent and a surfactant, and the mixture is uniformly mixed to obtain a microemulsion (ME agent).

Test Example 1 Antibacterial test against wood rot fungi (Ouensis and Kawatake). Sterile MDA medium (glucose 25 g, polypeptone 5 g, malt extract 10 g, magnesium sulfate 2 g, K ₂ HP
O ₂ 3g, agar 15g, distilled water 1 liter)
The test compound preparation prepared according to the above was added so as to have a concentration of 10 ppm, and poured into a petri dish having a diameter of 9 cm. After the medium was solidified, agar cultures of St. John's mushroom or Kawatake mushroom were inoculated in the center. After culturing this at 25 ° C. for 5 days, the flora diameter was measured, the rate of inhibition of mycelial growth was determined by the following formula, and the judgment was made according to the following criteria.

[0027]

(Equation 1) Criteria for A: Hyphal growth inhibition rate 100-90% B: Hyphal growth inhibition rate 89-80% C: Hyphal growth inhibition rate 79-50% D: Hyphal growth inhibition rate 49-0% The results are shown in Table 4. .

[0028]

[Table 13]

[0029]

[Table 14]

Test Example 2 Wood surface contaminants (Gliocladium v
Antimicrobial activity test against irens and Aspergillus niger). Example 2 was added to the MDA medium prepared in the same manner as in Test Example 1.
The test compound preparation prepared according to the above was added so as to have a concentration of 10 ppm, and poured into a petri dish having a diameter of 9 cm. After the medium has solidified, Gliocladium virens and Aspergil
A lua niger agar strip culture was inoculated. After culturing this at 25 ° C. for 5 days, the flora diameter was measured, the rate of inhibition of mycelial growth was determined, and the judgment was made according to the same criteria as in Test Example 1. The results are shown in Table 5.

[0031]

[Table 15]

[0032]

[Table 16]

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Yoshinobu Yamamoto 1-40-1-625, Mikadai, Kawachinagano, Osaka Minoru Fukada 2-11-3 Hattori-Honcho, Toyonaka-shi, Osaka F-term (reference) 4H011 AA02

Claims (4)

[Claims] 1. A compound of the general formula (I)[Wherein, R¹ And R^TwoMay be the same or different, and hydrogen
Atom, C₁-C₆Alkyl group, halo C₁-C₆Alkyl group, C_Three-C
₆Cycloalkyl group, C_Two-C₆Alkenyl group, C_Two-C₆Al
Quinyl group, cyano C₁-C₆Alkyl group, C₁-C₆Alkoxy
C₁-C₆Alkyl group, C₁-C₆Alkoxy C₁-C₆Alkoxy
C₁-C₆Alkyl group, phenyl C₁-C₆Alkyl group, same or
Has one or more halogen atoms on the ring which may be different
Phenyl C₁-C₆Alkyl group or 1,3-dioxolane-
2-Il C₁-C₆Represents an alkyl group;¹ And R^TwoIs together
Become-(CH_Two)_1-4-Or-CH (R^Three) -CH_Two-(Where R^ThreeIs hydrogen
Atom, C₁-C₆Alkyl group, halo C₁-C₆Alkyl group, C₁-C
₆Alkoxy group, halo C₁-C ₆Alkoxy group, C₁-C₆Al
Kirthio group, halo C₁-C₆Alkylthio group, cyano C₁-C₆
Alkyl group, cyclo C_Three-C₆Alkyl group, methylene group, C₁
-C₆Alkoxy C₁-C ₆Alkyl group, C₁-C₆Alkylthio
C₁-C₆Alkyl group, C_Two-C₆ Alkenylcarbonyloxy
C₁-C₆Alkyl group, phenyl group, same or different
, Halogen atom, C₁-C₆Alkyl group, halo C₁-C₆Al
Kill group, C₁-C₆Alkoxy group, halo C₁-C₆Alkoxy
Group, C₁-C₆Alkylthio group, halo C₁-C₆Alkylthio group
Or C₁-C _ThreeOne or more selected from alkylenedioxy groups
A substituted phenyl group having a substituent of phenyl C₁-C₆Al
A kill group, which may be the same or different, a halogen atom, C₁-C
₆Alkyl group, halo C₁-C₆Alkyl group, C₁-C₆Alkoki
Si group, halo C₁-C₆Alkoxy group, C₁-C₆Alkylthio
Group, halo C₁-C₆Alkylthio group or C₁-C_ThreeAlkylenedi
Having at least one substituent selected from oxy groups on the ring
Substituted phenyl C₁-C₆Alkyl group, pyridyl group, same or
May be different, halogen atom, C₁-C₆Alkyl group, ha
B c₁-C₆Alkyl group, C₁-C₆Alkoxy group, halo C₁-C₆
Alkoxy group, C₁-C₆Alkylthio group or halo C₁-C₆A
Having one or more substituents selected from alkylthio groups
Substituted pyridyl group, naphthyl group or the same or different
, Halogen atom, C₁-C₆Alkyl group, halo C₁-C₆Al
Kill group, C₁-C₆Alkoxy group, halo C₁-C₆Alkoxy
Group, C₁-C₆Alkylthio group or halo C₁-C₆Alkylthio
Substituted naphthyl having one or more substituents selected from
Represents a group. ) And X represents a carbon atom or a nitrogen atom.
You. ], Ketene S, S-acetals represented by
Industrial use characterized by containing salts as active ingredients
Fungicide. 2. R¹ And R^TwoTogether-(CH_Two)_1-4-
Or -CH (R^Three) -CH_Two-(Where R^ThreeIs a hydrogen atom, C₁-C₆Archi
Le group, halo C₁-C₆Alkyl group, C₁-C₆Alkoxy group, ha
B c₁-C₆Alkoxy group, C₁-C₆Alkylthio group, halo C₁
-C₆Alkylthio group, cyano C₁-C₆Alkyl group, cyclo
C_Three-C₆Alkyl group, methylene group, C₁-C ₆Alkoxy C₁-C
₆Alkyl group, C₁-C₆Alkylthio C₁-C₆Alkyl group,
C_Two-C₆Alkenylcarbonyloxy C₁-C₆Alkyl group,
A phenyl group, which may be the same or different, a halogen atom,
C₁-C₆Alkyl group, halo C₁-C₆Alkyl group, C₁-C₆Al
Coxy group, halo C₁-C₆Alkoxy group, C₁-C₆Alkyl
O group, halo C₁-C₆Alkylthio group or C₁-C_ThreeAlkylene
Substitution having one or more substituents selected from dioxy groups
Phenyl group, phenyl C₁-C₆Alkyl groups, identical or different
May be a halogen atom, C₁-C₆Alkyl group, halo C₁
-C₆Alkyl group, C₁-C₆Alkoxy group, halo C₁-C₆Al
Coxy group, C₁-C₆Alkylthio group, halo C₁-C₆Alkyl
Thio group or C₁-C_ThreeSelected from alkylenedioxy groups
Substituted phenyl C having one or more substituents on the ring₁-C₆Al
Kill group, pyridyl group, which may be the same or different, halogen
Atom, C₁-C₆Alkyl group, halo C₁-C₆Alkyl group, C₁
-C₆Alkoxy group, halo C₁-C ₆Alkoxy group, C₁-C₆A
Alkylthio group or halo C₁-C₆Selected from alkylthio groups
Substituted pyridyl groups having one or more substituents, naphthyl
Group or the same or different, a halogen atom, C₁-C₆
Alkyl group, halo C₁-C₆Alkyl group, C₁-C₆Alkoxy
Group, halo C₁-C₆Alkoxy group, C₁-C₆Alkylthio group or
Is Halo C₁-C₆One or more positions selected from alkylthio groups
A substituted naphthyl group having a substituent is shown. ) And X is charcoal
The industrial sterilization according to claim 1, which represents an element atom or a nitrogen atom.
Agent. 3. R ¹ and R ² together form -CH (R ³ ) -CH
_2- (wherein, R ³ may be a phenyl group or the same or different and a halogen atom, a C ₁ -C ₆ alkyl group, a halo C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a halo C ₁ A substituted phenyl group having at least one substituent selected from a -C ₆ alkoxy group, a C ₁ -C ₆ alkylthio group, a halo C ₁ -C ₆ alkylthio group and a C ₁ -C ₃ alkylenedioxy group.) And X
The industrial fungicide according to claim 2, wherein represents a carbon atom. 4. The industrial fungicide according to claim 1, wherein the industrial fungicide is a wood preservative.