JPH013164A - imine compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides a novel imine compound that is particularly useful as a fungicide.

(Prior Art and Problems to be Solved by the Invention) Conventionally, many imine compounds have been synthesized. For example, in Japanese Patent Application Laid-open No. 59-110601, the following -
Numerical formula (where n indicates the number of O~3, A is 710 Dan atoms,
A cyano group, nitro group, alkoxy group, alkoxycarbonyl group, etc. A2 represents a substituted or unsubstituted alkyl group, alkenyl group, phenyl group, etc., and X represents an oxygen atom or a sulfur atom. It is described that imine compounds represented by ) are useful as herbicidal antagonists. However, the compound represented by the general formula (2) described in the above document is completely different from the compound of the present invention in both its structure and usage, and the compound represented by the formula (2) is completely different from the compound of the present invention.
There was no mention of the bactericidal activity of the compound shown in 2).

(Means for Solving the Problems) The present inventors conducted research on imine compounds having high antibacterial activity. As a result, it was confirmed that a specific imine compound exhibits strong antibacterial activity against a wide range of bacterial species, including Escherichia coli, athlete's foot fungus, and sesame leaf blight fungus, making it an excellent bactericidal agent, leading to the completion of the present invention. .

That is, the present invention provides the formula (1) % formula % (wherein R represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R1 represents an alkyl group, and R2 represents a substituted or unsubstituted heteroaryl group). It is an imine compound represented by an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group.

In the present invention, the substituted or unsubstituted aryl groups represented by R and R2 in the above formula (1) can be used without particular limitation. Specific examples of such unsubstituted aryl groups include phenyl group and naphthyl group.

Examples include anthranyl group. Further, the type of substituent of the above-mentioned substituted aryl group is not particularly limited, but from the viewpoint of easy availability of raw materials, halodane atom, alkyl group, alkoxy group, alkylthio group, alkylamino group, nitro group, cyano group, and alkoxyalkyl group etc. are suitable. Specific examples of the above halodane atoms include chlorine, bromine, fluorine,
Each atom of iodine is mentioned. Preferred examples of the alkyl group include methyl group, ethyl group, n-propyl group, 1@o-propyl group, n-butyl group, etc. having 1 carbon number.
-4 alkyl groups are mentioned. In addition, some or all of the hydrogens in these alkyl groups may be substituted with a substituent such as a halodane atom, and specific examples include chloromethyl group, bromomethyl group, fluoromethyl group, iodomethyl group, dichloromethyl group, etc. group, difluoromethyl group, trichloromethyl group, trifluoromethyl group, chloroethyl group, fluoroethyl group, dichloroethyl group, )lifluoroethyl group, cyanmethyl group, hydroxymethyl group, and the like. Further, the alkoxy group mentioned above is not particularly limited, but specific examples include a methoxy group, an ethoxy group, and an n-propoxy group.

Representative examples include 1so-glopoxy group and n-butoxy group. Furthermore, the above alkylthio group is not particularly limited, but
Representative examples include methylthio group, ethylthio group, n-glopythio group, is.

-glopylthio group and the like. A specific example of the alkylamino group is a methylamine group.

Examples include dimethylamino group and diethylamino group.

Furthermore, the alkoxyalkyl group is not particularly limited. Specific examples thereof include methoxymethyl group, methoxyethyl group, methoxypropyl group, and ethoxymethyl group. The number of substituents in the substituted aryl group represented by R and R2 is preferably 1 to 3 from the viewpoint of easy availability of raw materials.

Furthermore, when there is a plurality of substituents, each substituent may be the same or different.

In the above formula (1), the substituted or unsubstituted heteroaryl group represented by R and R2 can be used without particular limitation. Specific examples of the unsubstituted heteroaryl group include furyl group, thienyl group, and pyrrolyl group.

Pyridyl group, benzofuryl group, benzothienyl group.

Examples include indolyl group, quinolyl group, and pyrazolyl group. Further, the types and number of substituents of the above-mentioned substituted heteroaryl group are the same as those exemplified for the above-mentioned substituted aryl group.

In the above formula (1), the alkyl groups represented by R1 and R2 are not particularly limited, and linear or branched alkyl groups are used. Further, the number of carbon atoms is not particularly limited, but it is preferably 1 to 6 from the viewpoint of easy availability of raw materials. Specific examples of the alkyl group include methyl group, ethyl group, n-
Propyl group, Imo-propyl group, n-butyl group, n
-hexyl group and the like. Further, as the substituted alkyl group represented by R2, all or part of the hydrogens in the above-mentioned unsubstituted alkyl group are an alkoxy group, an alkylthio group, a cyano group, an alkenyl group, an alkenyloxy group, an aryl group, or a heteroaryl group. It is preferable to replace the number with nine. Specific examples of such substituted alkyl groups include methoxymethyl group, ethoxymethyl group, and methoxymethyl group.
diethyl group, ethoxyethyl group, methoxyglovir group,
Allyloxyethyl group, methylthioethyl group, ethylthioethyl group.

Cyanmethyl group, cyanethyl group, allyl group, allyloxyethyl group, phenylmethyl group, 7! J-rumethyl group,
Examples include thienylmethyl group. In the case of an alkyl group substituted with an aryl or heteroaryl group, such as the phenylmethyl group, furylmethyl group, thienylmethyl group,
The nuclear aryl or heteroaryl group may have a substituent, and the conditions for the substituents of the substituted aryl group and heteroaryl group represented by R and R2 above can be applied as is.

The structure of the imine compound represented by formula (1) of the present invention can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), imine (C=
Absorption based on N) can be observed.

As a representative example, α-inpropyl-furfridene-N-
The infrared absorption spectrum of (benzenesulfonyl)amine is shown in FIG.

Measure the (I:I) mass spectral (MS) and find the composition formula corresponding to each observed peak (generally a number expressed as V, which is the ion mass number m divided by the ion charge number). By doing so, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. In other words, when a sample subjected to measurement is expressed using the general formula %, the molecular ion peak (hereinafter abbreviated as -) generally changes to the isotope abundance ratio depending on the number of halodane atoms contained in the molecule. Since the intensity ratio is observed accordingly, the molecular weight of the compound subjected to measurement can be determined. Further, for the compound represented by the above formula -, characteristic peaks corresponding to Mo (or M"'+1), y!3-8OR2, etc. are observed, and the bonding mode of the molecule can be known.

(c) 1H-nuclear magnetic resonance spectrum ('H-NMR
), it is possible to know the bonding mode of the hydrogen atoms present in the compound of the present invention represented by the above-mentioned formula. As a representative example of the H-NMR (δppm; tetramethylsilane standard, 11 L chloroform solvent) of the compound, the H-NMR of α-ingrobyl-fur7riden-N-(benzenesulfonyl)amine is shown in Figure 2. . The analysis results are shown below.

A double line corresponding to 6 protons was observed at 1.24 ppm, and can be attributed to the methyl groups (b) and (c). A multiplet corresponding to one proton was observed at 3.4 to 4.1 ppm, and can be attributed to the fo door (d). 6.4-6.6 ppm and 7.8-
8. Multiplets corresponding to one and two protons, respectively, were observed in lppm, and can be attributed to the protons substituted in the furan ring (1). 7.2-7.7ppm
A multiplet corresponding to five protons was observed in the figure, which can be attributed to the protons substituted in the benzene ring (,).

) Determine the weight percent of each of carbon, hydrogen, nitrogen, sulfur (and halodan if it contains halodan) by elemental analysis,
Furthermore, by subtracting the sum of the recognized weights of each element from 100, the weight percent of oxygen can be calculated and, therefore, the compositional formula of the compound can be determined.

The properties of the imine compound of the present invention vary depending on the types of R2H and R in the above-mentioned formula, but in general, it is a colorless, light yellow, light brown solid or liquid at normal temperature and normal pressure, and at a certain temperature If it becomes more than that, it tends to decompose.

The compounds of the present invention include benzene, ether, acetone, al3-, chloroform, acetonitrile, N, N-
It is soluble in common organic solvents such as dimethylformamide and dimethyl sulfoxide, but almost insoluble in water.

The method for producing the imine compound represented by formula (1) of the present invention is not particularly limited, and any production method may be used. A particularly preferred manufacturing method is as follows.

An imine represented by the general formula % formula % (2) (wherein, R represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R1 represents an alkyl group) and - formula % Formula % (3) (However, R2 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group, and 2 is a halodane atom.

08O2R or 0802CF. ) The imine compound represented by the above formula (1) can be obtained by reacting with the sulfonic acid halide or sulfonic anhydride represented by the formula (1).

In this reaction, the molar ratio of the imine and the sulfonic acid halide or sulfonic anhydride may be appropriately determined as necessary, but it is usually preferable to use equimolar amounts or a slight excess of the sulfonic acid halide or sulfonic anhydride. Common. In addition, it is generally preferable to use an organic solvent for the reaction, such as benzene, toluene, methylene ffl, or chloroform.

N,N-dimethylformamide and the like are preferably used.

Further, in the reaction, hydrogen halide or sulfonic acid is produced as a by-product. This hydrogen halide or sulfonic acid reacts with the imine represented by formula (2) in the reaction system, causing a decrease in the yield of the product. It is preferable to coexist with a sulfonic acid scavenger h0 The scavenger is not particularly limited and any known scavenger can be used, but generally preferred scavengers include trialkylamines such as trimethylamine and triethylamine; Pyridine; diazobicyclooctane; sodium alcoholade; sodium carbonate, potassium carbonate, and the like.

The order of adding the raw materials in the reaction is not particularly limited, but generally, the imine represented by formula (2) above is dissolved in a solvent and charged into a reactor, and the sulfonic acid halide represented by formula (3) dissolved in the solvent is added. Alternatively, it is preferable to add sulfonic acid anhydride while stirring.

Of course, it is also possible to continuously add raw materials to the reaction system and to continuously take out the generated reactants from the reaction system. The reaction temperature can be selected from a wide range, generally from -20°C to -150°C.
It is sufficient to select the temperature within the range of 0°C to 100°C. Although the reaction time varies depending on the type of raw material, it is usually sufficient to select it from the range of 5 minutes to 10 days, preferably 1 to 40 hours. Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and producing the desired product, ie, the imine compound represented by formula (1) above, from the reaction system is not particularly limited, and any known method can be employed. For example, after removing excess reaction reagents and generated salts from the reaction solution, the fi residue is extracted with an organic solvent such as benzene, toluene, or chloroform. The organic layer is dried with a drying agent such as Glauber's Salt or calcium chloride, and then the organic solvent is distilled off to obtain the desired product. Purification means may be carried out as required, and recrystallization, chromatography, vacuum distillation, etc. can be suitably used.

The imine compound represented by formula (1) of the present invention is:
Plant pathogenic bacteria such as rubber leaf blight and leaf wilt.

It has strong antibacterial activity against athlete's foot, Escherichia coli, Bacillus subtilis, etc., so it is useful as a disinfectant. These properties have not been observed in known imine compounds.

Compounds of the invention include, for example, Basidiomycetes and Fungi.

It can be widely applied to various pathogenic bacteria belonging to Ascomycetes, Deuteromycetes, Bacteria, etc.

The mode of use of the imine compound represented by formula (1) of the present invention is not particularly limited, and the mode of use of known herbicides can be used as is. For example, granules using an inert solid carrier, a liquid carrier, two emulsifying dispersants, etc.

Powder, emulsion, 2 tablets of water conservancy, oil, aerosol.

(Can be used in any dosage form such as a smoke agent. Of course, auxiliary agents for formulation, such as spreading agents, diluents, surfactants, etc., can also be added as appropriate.

(Examples) In order to explain the present invention more specifically, Examples will be described below, but the present invention is not limited to these Examples.

Example 1 47 g of 1,4-diazabicyclo-[2,2,2]octane L was processed into 10 g of a chloroform solution in which 1.50 g of α-isopropyl-furfridenamine was dissolved, and then 2.32 g of benzenesulfonyl chloride was dissolved. Twelve drops of chloroform solution were added dropwise.

- After stirring overnight, the reaction solution was poured into ice water and extracted with chloroform. After drying the chloroform layer over anhydrous sodium sulfate, chloroform was distilled off, and the residue was purified by silica dal chromatography (benzene/acetone) to obtain 1.16.9 light brown solid.

The results of measuring the IR of this material are shown in FIG.

Its elemental analysis values are C60, 43%, R5, 47%.

N4.98CH, composition formula C14H45NO3S (
C 60.63%, which is the calculated value for 277,34)
, R5,45%.

It was in good agreement with N5.05%. Further, when MS was measured, a peak corresponding to M0+1 was found at rrV/e278.

To m/e 136? Each peak corresponding to -5o() is shown. In addition, the results of measuring 'H-NMR (δ: ppm; monochloroform solvent based on tetramethylsilane) were as follows.

0°)(・) Shows a double line for 6 protons at 1,24 ppm, (
It corresponded to the methyl proton in b) and (c). 3.4~
The multiplet of one proton is shown at 4.1 ppm, and (d
) was equivalent to a proton. 6.4 to 6.6 ppm and 7.8 to 8.1 ppm, 1 and 2 zolotone, respectively.
The multiplet of (,) is shown and corresponds to the proton of the furan ring in (,).

A multiplet of 5 protons was shown at 7.2 to 7.7 ppm, which corresponded to the protons of the benzene ring in (,).

The above results revealed that the isolated product was α-ingrobyl-furfuritene-N-(benzenesulfonyl)amine. The yield was 38.3 cm.

Example 2 Various compounds represented by the following formulas, R-C=NSO2R2 (R, R', and R2 are shown in Table 1), were synthesized in the same manner as in Example 1. Table 1 shows the yield and single element analysis values of the synthesized compounds.

In addition, the abbreviations in Table 1 are as shown below.

Et; -c tyl group + n-Pr; normal propyl group.

imo-Pr: Isoglobil group, n-Bu: Normal butyl group, n-Pentyl: Normal bentyl group.

Application example ■: Heat sterilize a nutrient medium containing 5-chi agar at 121°C for 15 minutes, cool it to 50°C, and add pre-grown bacterial cells or spores suspended in sterile water. The mixture was mixed well, poured into a petri dish, and solidified into a flat plate.

A circular spout with a diameter of 8 cm was immersed in a methanol solution containing 15 of the compounds synthesized in Examples 1 and 2.
The excess was removed on a paper and placed on a solidified agar medium.

After culturing at about 30°C for 24-48 hours, the diameter of the blocking die was measured.

As a control bacterium and mold, Escherichia coli B
(Escherlchia colIB: EC)
z Bacillus subtilis
lls: BS), Aspergillus niger (
Aspergillus niger :AN).

Cochliobolus myapeanus (Cochliobol)
usmiyabeanu+s: CM) p) Triehophyton r
ubrum: TR), Fusarium oxysporum: F
O) was used. The results of the antibacterial test are shown in Table 2.

All of the test bacteria in Table 2 are indicated by abbreviations, and those that are ineffective or not tested are indicated by -.

[Brief explanation of the drawing]

1 and 2 show the IR and 'H-NMR spectra of the imine compound obtained in Example 1, respectively.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, R represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R^1 represents an alkyl group. and R^2 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group.