JPH0774131B2 - Fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a fungicide containing a silatrane compound represented by a specific structural formula as an active ingredient.

(Prior Art) With regard to organosilicon compounds, research has been repeated on synthesis and physiological activity. Among the organosilicon compounds, the present inventor has focused on a silatrane compound having an imino bond (C = N bond) in the molecule and synthesized various derivatives,
It has been found that a silatrane compound represented by the following structural formula has excellent antitumor activity, and has already proposed it (Japanese Patent Application No.
59-196813).

(Problems to be Solved by the Invention) However, no extensive research has been conducted on the synthesis and physiological activity of a silatrane compound having an imino bond in the molecule, and research in this field has been desired.

(Means and Effects for Solving Problems) For many years, the present inventor has synthesized many novel organosilicon compounds and has continued research on various physiologically active actions of the organosilicon compounds.

As a result, the present inventor has found that the silatran compound represented by the following general formula (1) exhibits excellent bactericidal activity, has completed the present invention, and has proposed it here.

That is, the present invention provides the following general formula (1) (However, R represents a hydrogen atom or an alkyl group, X represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, an alkylcarbonyl group, an alkoxycarbonyl group, a sulfo group, an alkylsulfonyl group, an alkoxy group,
An alkylthio group, a carboxyl group, a carboxamide group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy group, and Represents a group selected from a substituted or unsubstituted di (alkyl) amino group, n represents an integer of 1 or more, and m represents 0.
Or 1 is shown. ) Is a fungicide containing a silatran compound represented by the formula (1) as an active ingredient.

In the general formula (1), the number of carbon atoms of the alkyl group represented by R is not particularly limited, and a linear or branched group is used, but the number of carbon atoms is 1 to 6 because of easy availability of raw materials. Is preferred. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. In the general formula (1), among the substituents represented by X, specific examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms. As the alkyl group, the groups described for R above are preferably used. The number of carbon atoms of the alkenyl group is not particularly limited, and a linear or branched group is used, but the number of carbon atoms is preferably 2 to 6 from the viewpoint of easy availability of raw materials. Specific examples of the alkenyl group include a vinyl group, an allyl group and a butenyl group. Further, the number of carbon atoms of the alkynyl group is not particularly limited, and a linear or branched group is used, but it is preferable that the number of carbon atoms is 2 to 6 from the viewpoint of easy availability of raw materials. Specific examples of the alkynyl group include ethynyl group, propynyl group and butynyl group.

Preferable examples of the alkyl group constituting each group of alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, alkoxy, alkylthio, and di (alkyl) amino include the alkyl group having 1 to 6 carbon atoms as exemplified above for R.

Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group; specific examples of alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group. Specific examples of the (dialkyl) amino group include dimethylamino group, diethylamino group, dipropylamino group and dibutylamino group; specific examples of the alkylcarbonyl group include acetyl group, ethylcarbonyl group, propylcarbonyl group and alkoxycarbonyl group. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentoxycarbonyl group; specific examples of alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group and propoxy group. Sulfonyl group, a butyl sulfonyl group.

Further, as the substituents constituting the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, the substituted phenyl group, the substituted phenoxy group and the substituted di (alkyl) amino group, other than a hydroxy group, a nitro group, a cyano group, a sulfo group, etc. The halogen atom, the alkylcarbonyl group, the alkoxycarbonyl group, the alkylsulfonyl group, the alkoxy group, the alkylthio group, the alkyl group, the alkenyl group, the alkynyl group, the phenyl group and the like exemplified by X are used without particular limitation.
Specific examples of these substituents include a hydroxyethyl group,
Chloroethyl group, chloropropyl group, trifluoromethyl group, nitroethyl group, cyanoethyl group, benzyl group,
Phenylpropyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group,
Propoxymethyl group, propoxyethyl group, butoxymethyl group, butoxyethyl group, nitrovinyl group, cyanovinyl group, dichlorovinyl group, bis (β-chloroethyl)
Amino group, bis (β-hydroxyethyl) amino group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, hexylphenyl group, methoxyphenyl group, nitrophenyl group, cyanophenyl group, chlorophenyl group, bromophenyl group , A chloro (methyl) phenyl group, a methylphenoxy group, an ethylphenoxy group, a chlorophenoxy group, a bromophenoxy group, a nitrophenoxy group and the like.

In many cases, compounds having the groups listed above have various positional isomers, but the compounds are not particularly limited and can be used in the present invention. For example, as a methylphenyl group, o
-Methylphenyl group, m-methylphenyl group, and p-
Examples thereof include a methylphenyl group, and examples of the butyl group include an n-butyl group, a sec-butyl group, and a tert-butyl group.

In the general formula (1), n may be an integer of 1 or more, but n is an integer of 1 to 4, particularly n is an integer from the viewpoint of easy availability of raw materials.
It is preferably 1,3 or 4.

The silatrane compound represented by the general formula (1) used in the present invention is a crystalline solid having a constant melting point in most cases at room temperature and atmospheric pressure, and is rarely a viscous substance.
The method for producing the silatrane compound is not particularly limited, and a known method is preferably used, and the structure of the silatrane compound is generally confirmed by measuring elemental analysis, infrared absorption spectrum, mass spectrum, magnetic resonance spectrum and the like. can do.

The silatran compound used in the present invention exhibits an extremely broad and excellent bactericidal activity, as will be apparent from the examples described later.

The bactericidal activity is found in almost all of the silatran compounds represented by the above general formula (1).
By selecting the values of m and m, and the kind of the substituent X, very excellent activity is exhibited. Generally, those in which n is 3, those in which m is 0 or 1, and those in which R is a hydrogen atom or a methyl group tend to exhibit strong activity. As the substituent X, a halogen atom such as bromine or fluorine; an alkoxy group such as a methoxy group, an ethoxy group or a hexoxy group; an alkylthio group such as a methylthio group or an ethylthio group; a nitro group; a cyano group; a bis (alkyl) amino group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, substituted or unsubstituted phenyl groups, and substituted or unsubstituted phenoxy groups tend to show particularly excellent activity.

The silatrane compound of the present invention can be widely applied to a wide variety of pathogens belonging to, for example, basidiomycetes, soybean fungi, ascomycetes, incomplete fungi, and bacteria, and therefore, the activity of agricultural chemicals or pharmaceuticals. It can be said that it is extremely useful as a component.

Specific examples of the fungi in which the silatrane compound of the present invention exhibits extremely strong bactericidal activity include, for example, wilt fungus, sesame leaf blast fungus, vine blast fungus, Botrytis cinerea, white bacterium, Staphylococcus aureus and the like.

When the fungicide of the present invention containing the silatrane compound represented by the general formula (1) as an active ingredient is used as an agricultural fungicide, its concentration can be selected within a wide range depending on the object to be treated. For example, when treating plant parts, the concentration of the silatran compound may generally be used between 0.0001 and 1% by weight, preferably between 0.001 and 0.5% by weight. Further, when treating seeds, the silatran compound may be used generally in an amount of 0.001 to 50 g, preferably 0.01 to 10 g, per 1 kg of seeds. Further, when treating the soil, generally, the silatrane compound may be treated at the place of action so as to have a concentration of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight.

The mode of use of the bactericide of the present invention is not particularly limited, and the known mode of use of the bactericide can be used as it is. For example, granules, powders, etc. using an inert solid carrier, liquid carrier, emulsion dispersant, etc.
It can be used as an arbitrary agent such as an emulsion, a wettable powder, a tablet, an oil agent, an aerosol, and a smoke agent. Of course, auxiliary agents in the formulation, such as spreading agents, diluents, surfactants, solvents, etc., can be appropriately added.

The fungicide of the present invention can also be used by mixing it with an insecticide, another fungicide, another pesticide, a fertilizer substance, a soil conditioner and the like.

The following are production examples of the silatrane compound of the present invention and sterilization
The example which performed the fungicidal activity test is shown. However,
The present invention is not limited to these.

Reference Example 1 N- (p-ethoxycarbonylphenylmethylidene)-
γ-aminopropyltriethoxysilane (9.75g),
Liethanolamine (3.81 g), potassium hydroxide (0.30
Heat the mixture of g) and ethanol (30 ml) for 3 hours.
Melting point by recrystallization from ethanol after flowing
White crystals (5.09 g) at 131.5 to 133.5 ° C were obtained. The product
Infrared absorption spectrum was measured for 1710 cm
^-1To COOC₂H_FiveAbsorption based on carbonyl bond of group, 1640cm
^-1Shows absorption based on CH = N bond. Elemental analysis value
Is C56.93%, H7.18%, N7.00%, and C₁₉H₂₈N₂O_FiveSi
(392.52) is the calculated value for the composition formula C58.13%, H
The agreement was 7.19% and N 7.14%. Also, measure the mass spectrum.
When set, M to m / e391 -Peak corresponding to H, m / e
243 to M -C₆H_FourCOOC₂H_FivePeak corresponding to, m / e174 to N
(CH₂CH₂O)₃Si The peak corresponding to further¹³
As a result of measuring C-NMR, the observed peaks are as follows.
Assigned (chemical shift value δ, ppm).

From the above results, it was revealed that the obtained white crystal was N- (p-ethoxycarbonylphenylmethylidene) -γ-aminopropylsilatrane (Compound No. 8). The yield was 50.7%.

Reference Example 2 A mixture of γ- (2-aminoethyl) -aminopropyl silatrane (4.04 g), p-bromobenzaldehyde (2.72 g) and benzene (50 ml) was heated under reflux for 1 hour to produce water by azeotropic dehydration. To react. Volatile components were removed by vacuum distillation, and the residue was recrystallized from ethanol to give a white solid (5.16 g) with a melting point of 118-120 ° C. It was measured infrared absorption spectrum of the product, a broad absorption band based on the NH bond to 3430cm ^-1, and an absorption based on CH = N bond to 1640 cm ^-1. Its elemental analysis values are C49.05%, H6.50%, N9.58%, Br17.89%, S
i6.57% and calculated value for the composition formula C ₁₈ H ₂₈ N ₃ O ₃ BrSi (442.43) C 48.86%, H6.38%, N9.50%, Br18.06%, S
i agreed with 6.35%. Moreover, when the mass spectrum was measured, it was found to be m / e 245. Corresponding to the peak, at m / e 174 The peak corresponding to Then ¹³ C-NMR is measured,
The results of analyzing the spectrum were assigned as follows.

From the above results, the obtained product is N represented by the following formula.
-(P-Bromophenylmethylidene) -γ- (2-aminoethyl) -aminopropylsilatrane (Compound No. 2
8) was revealed. The yield was 79.3%.

Reference Example 3 According to the method of Reference Example 1, represented by the following general formula [p-
(Phenyl) -phenylmethylidene] γ-aminopropyl silatrane (Compound No. 1) was synthesized.

Example 1 A nutrient medium containing 1.5% agar was sterilized by heating at 121 ° C. for 15 minutes, then cooled to 50 ° C., and a suspension of pre-grown cells or spores in sterile water was added. It was mixed well, poured into a petri dish, and solidified into a flat plate. Reference example 3
A circular filter paper having a diameter of 8 mm was dipped in a methanol solution containing about 15% of the compound No. 1 compound synthesized in 1., the surplus was removed on the filter paper, and the plate was placed on a solidified agar medium. At about 30 ° C
After culturing for 24 to 48 hours, the diameter of the inhibition circle was measured. Cocliobolus Miyabenas (CM), Pericularia Sasaki (PS), Fusarium oxysporum (F)
O), Trichophyton mentaglophytes (TM), Trichophyton rubrum (TR), Microsporum gypseum (MG), Botrytis cinerea (BC), Staphylococcus aureus (SO), Aspergillus niger (AN) , Candida albicans (CA). The results of the antibacterial test are shown in Table 1. All the test bacteria in Table 1 are indicated by abbreviations.

From the above results, it was revealed that the compound of No. 1 exhibits excellent antibacterial activity.

Example 2 Compounds No. 8 and 28 obtained in Reference Example 1 and Reference Example 2 and the following general formula synthesized according to the method of Reference Example 1 and Reference Example 2 Example 1 using various silatrane compounds represented by
An antibacterial test was conducted in the same manner as in, and the diameter of the inhibition circle was measured. The results are shown in Table 2.

Table 2 shows R of the silatrane compound represented by the above general formula.
And the type of X, the values of n and m, the type of test bacteria, and the diameter of the inhibition circle. In Table 2, all of the test bacteria are indicated by abbreviations.

Claims (1)

[Claims] 1. A general formula (However, R represents a hydrogen atom or an alkyl group, X represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, an alkylcarbonyl group, an alkoxycarbonyl group, a sulfo group, an alkylsulfonyl group, an alkoxy group,
Alkylthio group, carboxyl group, carbamide group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted phenoxy group, and Represents a group selected from a substituted or unsubstituted di (alkyl) amino group, n represents an integer of 1 or more, and m represents 0.
Or 1 is shown. ) A fungicide containing a silatran compound represented by the formula (1) as an active ingredient.