JPS6157544A - Isophthalonitrile compound and nonmedical fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 and R2 are H, alkyl, alkenyl, (substituted) phenyl, residue of heterocyclic compound, etc.]. EXAMPLE:4-Amino-2,5,6-trifluoroisophthalonitrile. USE:A nonmedical fungicide. It has agricultural and horticultural bactericidal and fungicidal activity and broad bactericidal spectrum. It is also useful as a fungicidal and mildew-proofing agent for various industrial products and their raw materials. PREPARATION:The compound of formula I can be prepared by reacting tetrafluorophthalonitrile of formula II with the compound of formula III in a solvent or in the absence of solvent, at a temperature between -20 deg.C and the refluxing temperature of the solvent, optionally in the presence of a base (e.g. caustic alkali, triethylamine, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to an inphthalonitrile compound represented by the formula (I), and a non-medical disinfectant containing the compound as an active ingredient.

The compound of the present invention is not only useful as an agricultural fungicide, but also a novel compound that has not been described in any literature and is useful as a fungicide and fungicide for various industrial products and their raw materials.

R0 Prior Art and Problems It has been known that halogenated aromatic sonitrile exhibits biological activity as a fungicide, bactericide, nematode killer, and herbicide (Japanese Patent Application Publication Show 4l
-11358). Also, 4-alkoxy-2,5,6-
) Lichloroisophthalonitrile compound is known as an antifungal agent (Japanese Patent Publication No. 50-12142)
4).

In recent years, bacteria on various industrial products and their raw materials, etc.
Damage caused by microorganisms such as mold and yeast is considered a problem. These are harmful to aesthetics and health and hygiene, as well as deteriorating the performance and quality of industrial products.As a preventive measure, these substances have a large antibacterial and antifungal effect, exhibit a wide antibacterial spectrum, and are suitable for the purpose of the product. There is a need to develop antibacterial and antifungal agents that have various properties (water resistance, heat resistance, light resistance, degradability, stability, etc.).

Means for Solving Problems C1 The present inventors synthesized various inftaloniolyl compounds and developed antibacterial and antifungal agents for the purpose of developing a new antibacterial and fungicidal agent that satisfies the above requirements. While conducting research on the activity, we discovered that the compound of the present invention has excellent antibacterial and antifungal properties, and also that it has excellent properties as an agricultural fungicide, thereby completing the present invention.

Typical examples of the compounds of the present invention are shown in Table 1.
It's like this.

The general method for producing the compounds of the present invention will be explained in conjunction with the following formulas.

(II) (I[[) (1
) The compound (1) of the present invention can be prepared by mixing the starting materials (If) and (III) in a solvent or without a solvent.
is obtained. The reaction temperature is from -20°C to the reflux temperature of the solvent. As the reaction solvent, (II[) itself is used as a solvent, or an appropriate aprotic commercial medium such as acetonitrile chloroform, sochloroIthane, benzene, tolmenine, dioxane, ethyl ether, tetrahydrofuran, acetic ether, etc. is used. and use it.

Furthermore, in the above reaction, the reaction may be allowed to proceed by using a catalytic amount or a base in an equimolar to 10 times molar amount of (II). The base is appropriately selected from caustic alkali, triethylamine, pyridine, alkali carbonate, potassium fluoride and the like.

Note that the raw material tetrafluoroisophthalonitrile represented by the above general formula (II) can be obtained from tetrachloroisophthalonitrile by a known method [British Patent No. 1,026,290 (1966); Bull, Che.
m, Soc, Japan 40, 688 (196
6); Chemical Industry Magazine 2, 447 (1970); Japanese Patent Publication No. 11358/1983).

Next, a specific example of the method for producing the compound of the present invention will be shown.

Synthesis Example 1.4-Amino-2,5,6-)lifluoroisophthalonitrile (Compound &1) To a solution of 2.0 g of tetrafluoroisophthalonitrile and 2 Q ml of acetonitrile, add 28 polyammonium water Q and 5 m
1 was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then an aqueous sodium bicarbonate solution was added, extracted with chloroform, and washed with brine. After drying with sodium sulfate, chloroform was distilled off, and the obtained yellow crystals were recrystallized from chloroform to obtain 1.2 g of compound point 1. Yield 6
1ch.

19Fnmr (CCA4/DMSOd 6) δ25.
0(d, J, ,=9.4H2,IF)46.7(d,
J,, -18,81 (Z, IF) 80.0 (dd,
J,,=18.8Hz.

9.4Hz, IF)' Hnmr (CCl4/DMSOd6)δ2.8
(s) Synthesis Example 2.4-anilino-2,4,6-)rifluoroinophthalonitrile (Compound &6) Aniline 0.85 g is added to a solution of 2.0 g of tetrafluoroisophthalonitrile and 2.0 g of triethylamine in 3 QmJ of acetonitrile. ．． ! A solution of No. 9 in 20 ml of acetonitrile was added dropwise while stirring. After dropping, the mixture was stirred at room temperature for 1 hour, and the aqueous sodium bicarbonate solution was processed and extracted with chloroform. The chloroform extract was washed five times with an aqueous sodium chloride solution, dried over magnesium sulfate, and then the chloroform was distilled off.

The obtained crude crystals were purified by silica gel column chromatography (solvent: hexane) to obtain compound &612,39. Yield 87%.

19Fnmr (CCL4/DMSOd6) δ24.3(
d, JFF=9.4Hz, IF) 45-4 (d, J
yy=19.0Hz, IF)72.7(dd,
J,,=19.0Hz.

9.4Hz, IF) 1Hnmr (CC24/DMSOd6) δ3.7 (s
, IH) 7.4 (s, 5H) Synthesis Example 3. 4-noethylamino-2,5□6-drifluoroisophthalonitrile (Compound A 14 ) Synthesis Example 2
The resulting yellow liquid was distilled under reduced pressure to obtain Compound A 14k 2.01 as a fraction with a boiling point of 144-146°C/7 mmHg. Yield 91%.

"Fnmr (CC24/DMSO-db) δ23
．． 4(dd, J,,=9Hz +1.8Hz, IF
) 43.2 (aa, J,, = 18 Hz.

1.8Hz, IF) 69.5 (dddlJFF218H3゜9Hz, IF) 1Hnmr (CCA4/DMSO-δ6) δ1.2(t
, 3H) 3.4 (q, 2H) In the synthesis examples, Fnmr is a value measured using trifluoroacetic acid as an external standard, and 1Hnmr is a value measured using tetramethylsilane as an internal standard.

The base may be solid, liquid or gas, or a combination of these may be used.

Specific examples of solid bases include Merck, Clay,
Examples include kaolin, diatomaceous earth, calcium carbonate, potassium chlorate, silica, saltpeter, wood flour, nitrocellulose, starch, wheat flour, soybean flour, and gum arabic.

Examples of liquid bases include water and organic solvents.

The medium includes hydrocarbons such as benzene, toluene, xylene, kerosene, nosel oil, fuel oil, petroleum, and naphtha.

Ketones such as acetone, methyl ethyl ketone and cyclohexanone Ω. Chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, chlorethylene, amyl acetate and butyl acetate. Monoalkyl ethers of ethylene glycol, such as monomethyl ether, monoethyl ether, etc. Examples include alcohols such as methanol, ethanol, impropatol, and amyl alcohol.

Further, examples of the gas base include air, nitrogen, carbon dioxide, freon, pronokune, butane, and the like.

Furthermore, auxiliary agents (spreading agents, emulsifiers, dispersants, wetting agents, etc.) used in the formulation of the non-medical disinfectant of this invention include nonionic, anionic, cationic, and amphoteric surfactants. agent is used.

Example 1 Compounds listed in powder table 3 parts clay 40 parts talc 57 parts 'Example 2 Compounds listed in wettable powder table 75 parts Polyoxyethylene alkyl allyl ether 9
It goes without saying that the form of use of this invention is not necessarily limited to the above-mentioned agent.

The non-medical fungicide of this invention is effective in controlling a wide range of agricultural and horticultural crop diseases, and is also effective against microorganisms that adversely affect industrial products and materials, such as fungi, algae, bacteria, and slime. It is also effective against aircraft.

The main examples include the following two groups.

Group 1 (disease name) Paddy rice, rice blast, sesame leaf blight, branch blight, white leaf blight; barley wildfire;
Phytophthora; brown red part, rice cake, web mold, anthracnose, ring spot; beet leaf spot, brown spot, seedling damping-off; tomato blight, late blight, gray mold, leaf mold, wilt, sclerotia, seedling damping-off, ringworm; cucumber
Gray mold, downy mildew, gray blight, sclerotia, black star, seedling dieback, anthrax,
Vine blight, vine shaving; Radish black rot, stubble, yellowing, black spot, mildew; Onion stubble, downy rot, gray rot; Lettuce sclerotinia; Citrus gray mold, canker, black spot, I see. Diseases; Phosphorus monilia, black star, spotted defoliation; persimmon gray mold, okiya defoliation, corner defoliation, anthracnose; pear black star, black spot; peach gray mould, black star, phomopsis rot, borer bacterial disease Nivine downy mildew , black pox, botrytis, late rot, etc.

Group 2 (microorganisms that adversely affect industrial products and materials) Bacillus spp, l5taphyloco
ccua 5pp-rEscherichia 5pp
-r Pseudomonas 5pp-+5erra
tia 5pp-* Alternaria 5pp-
rAspergillus 5pp-r Penici
llium 5pp-rCladosporium 5
pp-r Mucor 5pp-) Rhizopua
5pp-r Gliocadium 5pp-rEu
rotium spp, r Aureobasidi
um 5pp-*Chaetomium spp, r
Fuaarium app, rMyrotheci
um app, r Rhodotorula spp.
, rSaccharomyceg 5pp-a The non-medical disinfectant of this invention has an active ingredient concentration of 1 to 1000 ppm, preferably 10 to 1000 ppm, depending on the type of microorganism.
When used at a concentration of 500 ppm, it can not only control plant diseases but also protect industrial products and materials from damage by microorganisms.

The active ingredients of the non-medical fungicide according to the present invention can be used alone as described above, as well as various insecticides, fungicides, herbicides, plant growth regulators, acaricides, and nematicides. A wide range of effects can be expected by mixing it with agents, attractants, repellents, plant nutrients, fertilizers, and soil structure improvers.

In addition to the above-mentioned agricultural and horticultural disinfectants, the non-medical disinfectant according to the present invention can be used for industrial products and materials that can be adversely affected by microorganisms, such as plastics, plasters, carpet adhesives, emulsions, paints, etc. Coatings, leather, glue, wood, textiles, paper and cardboard can be protected from microbial attack or destruction. In connection with industrial materials, mention may also be made of parts of production plants, such as cooling water circulation systems and cooling lubricant circulation systems, which are adversely affected by microorganisms.

21 Effects of the Invention Below, representative test examples will be shown to specifically explain the effects of the compounds of the invention. However, these are merely examples, and it goes without saying that the application examples of the present invention are not limited to these.

Test Example-1 Test method for antibacterial activity against plant pathogenic bacteria> Conidia of plant pathogenic bacteria cultured in a specified medium are uniformly mixed in a PSA medium, and a certain amount is poured into a specified container to form a uniform plate. . After solidification, a door paper with a diameter of 8 mm that has absorbed a certain amount of the drug at a predetermined concentration and air-dried is placed on it, and the diameter of the inhibition circle produced after 48 hours of culture is measured.

However, the number of stations shall be two.

Test results> B, c: Vegetable gray mold fungus A, k: Pear black spot fungus P-o: Rice blast fungus X, c: Citrus fungus test example-2 Pear black spot efficacy test Test method> Pear ( As a development plan for cultivar: Nijisseiki, a chemical solution diluted to a predetermined concentration was sprayed at 20 Ttl per 5 leaves and air-dried indoors.

Alternaria K cultured in apricot medium after air drying
Conidia of C. ilcuchiana were inoculated by spraying and immediately left to stand for 3 days at 25° C. and humidity of 100° C. After 3 days, the affected area was examined.

However, the number of runs shall be 5.

Test results> Test Example-3 Antibacterial spectrum test on spores using agar dilution streak method After pouring 10 M of Jabuimo agar medium containing each drug at a predetermined concentration into a Petri dish and solidifying it, each test sample was cultured in the same medium in advance. Fungal spore suspension (40 spores 15<400
(1 field of view) 1 kl platinum loop was inoculated in a streak pattern and left in a constant temperature room at 28° C. for 3 days, and then the presence or absence of growth was examined and the minimum inhibitory concentration (MIC) was measured.

However, the number of runs shall be 4.

Test results> Bacterial name A: Penicillium funcu
losumB: Aspergillus nige
rC: F/usarium proliferatu
mD: Gliocladium virensE゛: Rh1zopus 5toronifer test example-
4 Antibacterial spectrum test on hyphae using agar dilution method The tip of the bacterial flora of each test bacterium cultured on Noyaga 1 Mo agar medium containing a prescribed concentration of each drug was punched out using a cork gouger with 8 fins in diameter. After inoculating the seeds on the top and leaving them in a constant temperature room at 28° C. for 3 days, the presence or absence of growth was investigated and the minimum inhibitory concentration (MIC) was measured. However, the number of runs shall be 4.

Test results> Test Example-5 Antibacterial spectrum test against bacteria using agar dilution streak method A normal bouillon agar medium containing each drug at a predetermined concentration was poured into a Petri dish, solidified, and then carefully poured into the same liquid medium. The cultured bacterial cell suspension was inoculated in a striped loop and left in a constant temperature room at 30° C. for 2 days, and then the presence or absence of growth was examined and the minimum inhibitory concentration (MIC) was measured. However, the number of runs shall be 4.

Test results> Bacteria name

Claims (2)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 and R_2 are the same or different groups, including hydrogen, alkyl group, alkenyl group, alkynyl group, even if substituted. It may represent a phenyl group, or the residue of a heterocyclic compound, or may form the residue of a heterocyclic compound with ▲ there are mathematical formulas, chemical formulas, tables, etc. ] Isophthalonitrile compound. (2) A non-medical disinfectant containing the isophthalonitrile compound according to claim 1 as an active ingredient.