JPH0543558A - Halopropargyl mercaptotriazole compound, composition containing same, use thereof and preparation thereof - Google Patents

Abstract

PURPOSE: To provide a new compound useful as microbiocides and fungicides in a wide range of fields.

CONSTITUTION: The compound of formula I (A is H, an alkyl, aryl, heterocycle; R is an alkyl, alkenyl, alkynyl, phenyl, heterocycle; X is a halogen), e.g. 3-(3- iodopropargyl)mercapto-4-phenyl-1,2,4-triazole, is obtained by allowing the compound of formula II to react with a halogenating agent (e.g. N-iodosuccinimide) in a solvent (e.g. acetone) at 0-25°C for 20 min-24 hrs. The compound has the ability to control or protect from microorganisms such as fungi, bacteria, algae, virus and yeast. The compositions containing the compound of formula I and agricultural carriers, cosmetics, cutting oils, soaps, synthetic detergents, stabilizers, film forming materials, etc., can be protected from microorganisms.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to controlling microorganisms.

Description of the Prior Art Although certain heterocyclic iodopropargyl compounds have been proposed as fungicides or microbicides, these types of compounds have not been commercially successful.

Chemical Abstracts, 72: 3169
In 6X (1970), the following equation:

[Chemical 3] The synthesis of 2- (3-iodo-2-propynylthio) benzimidazole, -benzothiazole and benzoxazole is shown.

US Pat. No. 4,17 to Brandman et al.
0,704 discloses iodopropargylpyridyl and picolinyl ethers and thioethers as antibacterial agents.

Edwards US Pat. No. 4,616,616
In No. 004, the following formula:

[Chemical 4] Fungicidal activity is disclosed for compounds of

Rose US Pat. No. 4,639,460
In the issue, the following formula:

[Chemical 5] Are listed as fungicides.

Schmitt US Pat. No. 4,520,
In No. 023, 3- (3-iodopropargyl)
Benzo-1,2,3-triazolin-4-ones have been shown and their use as microbicides.

The prior art does not suggest that compounds within the scope of the formula of the present invention have utility in controlling microorganisms.

SUMMARY OF THE INVENTION It is an object of the present invention to provide novel compounds for controlling microorganisms.

A further object is to provide methods of making such compounds, methods of using them, compositions containing such compounds and methods of using such compositions.

These and other objects that will become apparent from the description below are achieved by the present invention.

The present invention, in one aspect thereof, is of the formula:

[Chemical 6] (Wherein A is selected from the group consisting of hydrogen, alkyl, aryl and heterocyclic groups; R is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted Or unsubstituted phenyl and a substituted or unsubstituted heterocyclic group; X is selected from the group consisting of halogen).

Another aspect of the invention is the following formula:

[Chemical 7] And a method of producing such a compound, which comprises reacting the compound of claim 1 with a halogenating agent.

A further aspect is the use of compositions containing such compounds, or the compounds themselves, for wood, paints, adhesives, glues, papers, fabrics, leather, plastics, cardboard, lubricants, cosmetics, foods, caulks. It covers the protection of agents, feeds and industrial cooling water from microorganisms.

Detailed Description of the Preferred Embodiments The compounds of the present invention are of formula (I) set forth above.
In a more preferred embodiment, A is hydrogen; C₁ ~ C₁₈Straight chain or
Branched chain alkyl; C₃ ~ C₈ Cycloalkyl; C₃ ~ C
₆ Alkenyl; C₃ ~ C_Five Alkynyl; C₇ ~ C₁₂Ara
Rukiru; C₆ ~ C₁₂Aryl; halogen, C₁ ~ C_Four A
Rukiru, C₁ ~ C_Four Alkoxy, nitro, cyano, cal
Boxil, C₁ ~ C_Four Alkoxycarbonyl, C₁ ~ C
_Four Alkylthio, -S (O)_n R² (Where n is 1 or
Is 2 and R² Is C₁ ~ C_Four It ’s an alkyl)
Substituted with 1 to 3 substituents selected from the group
C₆ ~ C₁₂Aryl; and halo-substituted, nitro-substituted or
Unsubstituted 2-thienyl, 3-thienyl, 2-furyl, 3
-Furyl, 2-pyridyl, 3-pyridyl and 4-pyridy
A group selected from the group consisting of;
It is a compound that is

Preferred examples of A are hydrogen, 4-chlorophenyl, 3-chlorophenyl, 2-methylphenyl, 4-
Methylphenyl, 3-methylphenyl, 2-thienyl,
2-nitrophenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 4-bromophenyl, 2-fluorophenyl, 2-chloro-4-nitrophenyl , 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, methyl, iodopropargyl, t-butyl, phenyl, 4-
Nitrophenyl, 3-fluorophenyl, 1-naphthyl, 2-naphthyl, 3-pyridyl, 3-bromophenyl, 3-ethoxyphenyl, n-propyl, 2-chlorophenyl, cyclohexyl and 2-furyl.

Suitable examples of R include methyl, ethyl, isopropyl, n-butyl, phenyl, 4-chlorophenyl,
Allyl, 2-propynyl, 2-furyl, 2-thienyl,
3-iodo-2-propynyl, 3-nitrophenyl, 3
-Methoxyphenyl and 4-methylphenyl.

R is also hydrogen; C ₁ To C ₁₈ straight or branched chain alkyl; C ₃ ~ C ₈ Cycloalkyl; C ₃ ~ C ₆
Alkenyl; C ₃ ~ C ₅ Alkynyl; C ₇ ~ C ₁₂ Aralkyl; C ₆ To C ₁₂ aryl; halogen, C ₁ ~ C ₄ Alkyl, C ₁ ~ C ₄ Alkoxy, nitro, cyano, carboxyl, C ₁ ~ C ₄ Alkoxycarbonyl, C ₁ ~ C ₄
Alkylthio, -S (O) _n R ² (Where n is 1 or 2
And R ² Is C ₁ ~ C ₄ C ₆ substituted with 1 to 3 substituents selected from the group consisting of
C ₁₂ aryl; and a group selected from the group consisting of halo-substituted, nitro-substituted or unsubstituted 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl; May be.

Preferred are iodopropargyl compounds, ie those in which X is I.

As described above, a compound of formula (I) and an agriculturally acceptable carrier, cosmetic agent, cutting oil,
Compositions containing any of soaps or synthetic detergents, stabilizers, film-forming materials, etc. protect against or protect against a wide variety of microorganisms including fungi, bacteria, algae, viruses and yeasts. It has a wide range of utilities to control. Preferred uses of the composition are wood, paints, adhesives,
Protecting glue, paper, cloth, leather, plastic, cardboard, lubricants, cosmetics, foods, caulks, feeds and industrial cooling water from microorganisms.

The following are specific industries and uses for the compounds or compositions of the present invention.

Industrial applications Adhesives, sealants Adhesives, caulks, sealants. Agricultural / Food Chain Supplemental Preservation, Agricultural Active Ingredients, Preservation of Agrochemicals, Preservation of Agricultural Formulations, Preservation of Animal Feed, Preservation of Dairy Chemicals, Fertilizers, Preservation of Foods, Preservation of Food Processing Chemicals, Grains , Post-harvest crop protection, sugar processing, tobacco. Construction products Asphalt / concrete, cement modifiers, construction products, roof mastics, synthetic plaster, wall mastics, joint cements. Cosmetics and toiletries Cosmetics, raw materials for cosmetics and toiletries, toiletries. Disinfectant, disinfectant Disinfectant, disinfectant Emulsion, dispersant Aqueous dispersant, dispersed pigment, latex, photographic emulsion, pigment slurry, polymer latex. Household compound products Softeners for fabrics, brighteners, waxes, hand dish cleaners, raw materials, liquid cleaners, hand soap. Industrial processing Others Electrodeposition paint, bath, rinse, pre-treatment for electrodeposition, post-rinse, preservation of industrial liquid products, pasteurization bath, preservation of treatment aids. Industrial water treatment Air cleaning, cooling towers, cooling water, water cooling, preservation / treatment of thin plates and structural members for wooden cooling towers, canisters, pasteurization in brewing, closed loop water cooling systems. Laundry Household laundry products, laundry products, laundry water, sanitary items. Leather, leather products Leather, leather products. Lubricants, hydraulic aids Automotive lubricants and fluids, conveyor lubricants, greases, hydraulic fluids, lubricants. Medical instruments diagnostic enzymes, diagnostic kits, medical instruments. Metal working and related applications Cutting oil, metal cleaning, metal working fluid. Odor control (active ingredients) Air conditioning, animal litter, cat litter, sanitary chemicals, deodorants, humidifiers, industrial deodorants, hygiene formulations, toilet bowls. Paints and coatings Emulsions, paints. Paper and wood pulp, their products Absorption materials for paper and wood pulp, packaging materials for paper and wood pulp, paper, paper products, paper processing, sack packaging, wood pulp, wood pulp products. Paper mills Paper mills Anti-adhesives (slimicides), pulp and paper slurries. Petroleum refining, fuels Aviation fuel (jet fuel, aviation gasoline), crude oil, burner, diesel and turbine fuel oil, coal slurry, diesel fuel additive, diesel fuel, fuel, gasoline, heating oil, hydrocarbons, kerosene, liquefaction Storage, transportation and manufacturing of petroleum gas, petrochemical raw materials, petroleum products, recycled petroleum products, residual fuel oil, turbine oil. Photographic chemicals and processing Photoprocessing: Wash water, rinses, light treatments, photoprocessing chemicals (developer, stabilizer, etc.). Printing Ink solution (for printing), ink components (such as pigments, resins, solvents), ink. Disinfectant (active) Disinfectant, dairy disinfectant, tooth disinfectant, fermentation disinfectant, food disinfectant, food disinfectant, medical disinfectant, stucco disinfectant, veterinary disinfectant Agent. Soaps, detergents, cleaning agents Cleaning agents, detergents, household cleaning agents, industrial cleaning agents, liquid soaps, oil and grease removers, powder soaps, raw materials for cleaning products, soaps, and surfactants. Textiles, textile products Adhesive fabrics, burlaps, canvas, canvas products, carpet backings, carpets, garments, coated fabrics, curtains, draperies, engineering fabrics, textiles, geotextiles, woven fabrics. Products, knitted fabrics, nets, non-woven fabrics, strings, rugs, textile accessories, textile products, textiles, upholstery materials, woven fabrics, yarns. Fabric processing Dye fixing agents, dyes, fiber lubricants, texture modifiers, sizing agents, fabric processing liquids. Treatment (active ingredient or preservation) Animal health / veterinary medicine, aquatic culture, dentistry, human health, pharmacy / therapeutics. Water purification Activated carbon bed, deionized resin, filter, membrane, reverse osmosis membrane, ultrafiltration membrane, water purification, water purification pipe, pipe. Application to wood Lasures, wood, wood products. Others Bedding containing alcohols, water or gel, ceramics, contact lenses: Cases / filtration, electronic circuits, chemical substances for electronic products, enzymes for food manufacturing, enzymes, industrial enzymes, gel cushions, marine antifouling agents, white Oilfield jets such as mold control agents, wood, plastics, laundry, mining, natural rubber latex, improved recovery jets, drilling fluids, breaking waters and finished fluids, pipes, plastics, polymer systems, polymers and resins (synthetic and Natural), reagent storage, rubber, rubber products, skin removers, solid protective / decorative films, tinting, swimming pools, waste disposal, waterbeds.

The amount of compound used depends on the application. Useful amounts for particular applications are comparable to those used for other microbicidal compounds.

The compound can be used in combination with other microbicides. Here, the term "microbicide" is equivalent to "antimicrobial agent" as used herein.

The compounds of formula (I) can be prepared by various methods. One suitable method is the following formula:

[Chemical 8] A method comprising reacting the compound of 1) with an iodizing agent or a brominating agent.

Suitable iodizing agents or brominating agents include
For example, iodine, bromine, iodine / amino compounds such as morpholine / iodine complex, N-bromosuccinimide (NBS) and N-iodosuccinimide (N
IS) and the latter is most preferred.

If iodine, bromine or iodine / amino compounds are used, hydroxides of bases, preferably sodium or potassium, must also be used, and solvents such as methanol, ethanol and aqueous ethanol must also be used. I have to.

If NIS or NBS is used, a catalyst such as silver nitrate must be used in the presence of a solvent such as acetone, methyl ethyl ketone, tetrahydrofuran and the like.

At reaction temperatures of about 0 ° C. to about 25 ° C., reaction times of about 20 minutes to about 24 hours are preferably utilized.

Another suitable method for obtaining compounds of formula (I) is to use a halopropargylating agent such as a compound of formula (III) in the presence of a base such as potassium carbonate and a solvent such as acetone. And a method of obtaining from the compound of formula (II).

[0031]

[Chemical 9]

The meanings of A, R and X are as defined above. L is a dissociative group such as bromine or chlorine, or O
--SO ₂ --R (wherein R is methyl or phenyl or p--
It is a trill). Examples of compounds of formula (III) include 3-iodopropargyl chloride, 3-iodopropargyl mesylate and 3-iodopropargyl-p.
-Toluene sulfonate. The reagent of formula (III) can also be prepared by the methods described in the literature.

Applying a compound of formula (I), fungi, bacteria,
Suitable methods for controlling algae, viruses, yeasts, etc.
Similar to methods well known in the art with amounts and carriers.

The following examples illustrate some aspects of the present invention. All parts and percentages are by weight unless otherwise indicated.

EXAMPLES Some representative examples of compounds of the invention are shown below. Compound 1: 3- (3-Iodopropargyl) mercapto-4-phenyl-1,2,4-triazole; Compound 2: 3- (3-Iodopropargyl) mercapto-4- (4-chlorophenyl) -1,2, 4-triazole; Compound 3: 3- (3-Iodopropargyl) mercapto-4-methyl-5-phenyl-1,2,4-triazole; Compound 4: 3- (3-Iodopropargyl) mercapto-4- (2 -Chlorophenyl) -1,2,4-triazole; compound 5: 3- (3-iodopropargyl) mercapto-4- (4-methoxyphenyl) -1,2,4-triazole; compound 6: 3- (3- Iodopropargyl) mercapto-4- (4-methylphenyl) -1,2,4-triazole; compound 7: 3- (3-iodopropargyl) Compound 8: 3- (3-iodopropargyl) mercapto-4- (n-hexyl) -1,2,4-triazole; compound 9: lucapto-4- (3-chlorophenyl) -1,2,4-triazole; 3- (3-Iodopropargyl) mercapto-4- (n-butyl) -1,2,4-triazole; Compound 10: 3- (3-Iodopropargyl) mercapto-4- (4-chlorophenyl) -5-methyl -1,
2,4-triazole; compound 11: 3- (3-iodopropargyl) mercapto-4-phenyl-5-methyl-1,2,4-triazole; compound 12: 3- (3-iodopropargyl) mercapto-4, 5-Diphenyl-1,2,4-triazole; Compound 13: 3- (3-Iodopropargyl) mercapto-4- (n-heptyl) -1,2,4-triazole; Compound 14: 3- (3-Iodo Compound 15: 3- (3-iodopropargyl) mercapto-4-cyclohexyl-1,2,4-triazole; propargyl) mercapto-4- (n-octyl) -1,2,4-triazole;

Table 1 shows the structure and physical data of these representative compounds. Table 1 Physical data Compound AR Melting point (° C) or NMR chemical shift (ppm) 1 H phenyl 161-163 ° C 2 H 4-chlorophenyl 174-175 ° C 3 Phenyl methyl 142-146 ° C 4 H 2-chlorophenyl 65-70 ° C 5 H 4-methoxyphenyl 125-136 ° C 6 H 4-methylphenyl 165-170 ° C 7 H 3-chlorophenyl 170-173 ° C 8 H n-C ₆ H ₁₃ 8.70 (1H, s) 4.07 (2H, s) 4.00 (2H, t) 1.70 (2H, m) 1.40-1.10 (6H, m) 0.86 (3H, t) 9 H n-C ₄ H ₉ 8.24 (1H, s) 4.08 (2H, s) 4.00 (2H, t) ) 1.80 (2H, tt) 1.50-1.10 (2H, m) 0.90 (3H, t) 10 methyl 4-chlorophenyl 7.78-7.50 (4H, q) 4.04 (2H, s) 2.26 (3H, s) 11 methyl phenyl 165 -167 ℃ 12 Phenyl Phenyl 164 ℃ 13 H n-C ₇ H ₁₅ 8.24 (1H, s) 4.08 (2H, s) 4.00 (2H, t) 1.80 (2H, tt) 1.50-1.10 (8H, m) 0.90 ( 3H, t) 14 H n-C ₈ H ₁₇ 8.22 (1H, s) 4.10 (2H, s) 4.00 (2H, t) 1.79 (2H, tt) 1.50-1.10 (10H, m) 0.90 (3H, t) 15 H cyclohexyl 120-125 ℃

Example 1 Preparation of 3- (3-iodopropargyl) mercapto-4-methyl-5-phenyl-1,2,4-triazole (Compound 3)

(A) Preparation of 1-benzoyl-4-methylthiosemicarbazide A suspension of benzoic acid hydrazide (6.8 g, 0.05 mol) in tetrahydrofuran (75 ml) at room temperature with magnetic stirring was added tetrahydrofuran ( A solution of methylisocyanate (3.7 g, 0.05 mol) in 5 ml) was added via dropping funnel. After the addition was completed, 3 drops of triethylamine was added as a catalyst. The reaction mixture turned into a very thick paste after about 5 minutes. The reaction mixture was stirred at room temperature for 1 hour. Hexane (100 ml) was added,
The white precipitate obtained was collected by suction filtration and washed with some hexane to give 7.0 g of 1-benzoyl-4-methylthiosemicarbazide. Melting point 197-200
° C. NMR spectrum (DMSO-d ₆ Middle) indicated the desired compound.

(B) 3-phenyl-4-methyl-1,
Preparation of 2,4-triazoline-5-thione Sodium hydroxide (1.15 g, 28.7 mmol) was dissolved in water (50 ml). In this basic solution, 1-
Benzoyl-4-methylthiosemicarbazide (6 g, 2
8.7 mmol) was added. The resulting clear solution was gently refluxed on a heating mantle for 2 hours with magnetic stirring. The reaction mixture was cooled to room temperature and neutralized to pH-5 with concentrated hydrochloric acid. The white precipitate was collected by suction filtration, washed with water and 4.1 g of triazoline-5-thione (yield 7
4.8%) was obtained as a white powder. Melting point 166-16
8 ° C. NMR spectrum (DMSO-d ₆ Middle) indicated the desired compound.

(C) 3-Propargyl mercapto-4-
Preparation of methyl-5-phenyl-1,2,4-triazole 3-phenyl-4-methyl-1,2,4-triazoline-5-thione (3.1 above) in acetone (40 ml).
g, 16.23 mmol) at room temperature under nitrogen with magnetic stirring under anhydrous potassium carbonate (2.76 g, 20
), Followed by propargyl bromide (2.7 g of 80% solution in toluene, 18 mmol). The reaction mixture is
Reflux on a heating mantle for 16 hours. The mixture was cooled to room temperature and the solids were filtered off by suction filtration. The filtrate was concentrated on a rotary evaporator to an oily residue. The residue was further purified by short column silica gel eluting with ethyl acetate / hexane (1: 1 to 3: 1, total 800 ml) to give 3-propargylmercapto-4-methyl-5-phenyl-1,2,4-triazole. 2.8 g (yield 7
5.3%) was obtained as a yellow viscous oil. NMR spectrum (DMSO-d ₆ Middle) indicated the desired compound.

(D) Preparation of 3- (3-iodopropargyl) mercapto-4-methyl-5-phenyl-1,2,4-triazole (compound 3) 3-propargylmercapto-4 in dry acetone (20 ml). To a solution of -methyl-5-phenyl-1,2,4-triazole (2 g, 8.73 mmol) at room temperature with magnetic stirring silver nitrate (100 mg, 0.58 mmol), then N-iodosuccinimide ( 2 g, 8.8 mmol) was added. After stirring for 1 hour, the resulting cloudy mixture was diluted with some acetone and the solids were filtered off by suction filtration. The filtrate was concentrated to a residue. Ethyl acetate (200 ml) was added, and the mixture was washed with water (50 ml twice) and brine (50 ml three times). The organic phase was dried over sodium sulphate. Filtered and concentrated to give a yellow residue. The residue was slurried with hexane and suction filtered to give 3- (3-iodopropargyl) mercapto-4.
1.9 g (yield 61.5%) of -methyl-5-phenyl-1,2,4-triazole (Compound 3) was obtained as a yellow solid. Melting point 142-146 [deg.] C. NMR spectrum (DMSO-d ₆ Middle) indicated the desired compound.

Example 2 3- (3-Iodopropargyl) mercapto-4- (n
-Octyl) -1,2,4-triazole (Compound 1
4) Manufacturing

(A) Preparation of 3-iodopropargyl mesylate A solution of 3-iodopropargyl alcohol (5 g, 27.5 mmol) in methylene chloride (150 ml) was charged with 0.
Triethylamine (2.8 g, 2
7.5 mmol) was added. Methanesulfonyl chloride (3.2 g, 27.5 mmol) was added dropwise to the above solution with magnetic stirring. The reaction mixture was stirred at 0-5 ° C for 2 hours. The reaction mixture was added with 0.5 N HCl (50 m
l), dilute sodium carbonate (50 ml), water (3 times 50 ml) and brine. The organic phase is MgSO ₄ Dried above and filtered. The filtrate was concentrated on a rotary evaporator to give 5.5 g of product (76.9% yield) as a tan oil. ¹ H-NMR spectrum (CDC
l ₃ ) was consistent with the desired compound. This compound
Used in the following step without further purification.

(B) 3- (3-Iodopropargyl) mercapto-4- (n-octyl) -1,2,4-triazole (preparation of compound 14) 4-n-octyl-1,2 in dry acetone. , 4-Triazoline-5-thione (2 g, 12.55 mmol) in potassium carbonate (1.8 g, 13.0 mmol) followed by 3-iodopropargyl mesylate (3.
4 g, 13.18 mmol) was added at room temperature. The reaction mixture was stirred at room temperature for 20 hours. The obtained solid content was filtered by suction filtration, and the filtrate was washed with water and brine. The organic layer was filtered and dried over MgSO _4. The filtrate was concentrated on a rotary evaporator to give a brown oil. The pure compound was obtained by column chromatography on silica gel eluting with ethyl acetate to give 1.8 g (38% yield) as a light brown oil. The NMR spectrum showed the desired compound. Elemental analysis: Calculated value for C ₁₃ H ₂₀ IN ₃ S: C = 41.4%, H = 5.30%, S = 8.30
%, I = 33.6%. Analytical value: C = 42.03%, H =
5.46%, S = 8.56%, I = 33.4%.

Example 3 Biocidal evaluation of compounds The minimum inhibitory concentration (MIC) is obtained by a 2-fold serial dilution test using broth. The test is conducted as follows. A stock solution or dispersion of the test compound, typically at a concentration of 1%, is prepared in a 5: 3: 2 solvent solution of acetone, methanol and water. An aliquot of stock solution is dispensed into the culture medium to give an initial starting test concentration of 250 ppm of compound.

When the test is ready, an equal volume of compound-free broth is placed in each container of the serial dilution except the first container. The first vessel contains 2 volumes of broth with a starting concentration of test compound. Transfer 1/2 of the broth from the first container to the second container. After mixing, 1/2 of the volume obtained is removed from the second container and transferred to the third container. 250, 125, 63, 31, 1
6, 8 and 4, 3, 1, 0.5, 0.25 and 0.12.
Repeat all cycles until a series of concentrations in ppm is given.

Each container is then inoculated with a cell suspension of the appropriate test organism. Bacteria are grown in broth and fungi on agar slant for a time and temperature appropriate to the species being tested. At the end of the growth time, the broth is swirled to disperse the cells. In the case of fungi, spores are collected by pipetting water onto the slant and removing the spores with a sterile loop. Normalize the cell / spore suspension by controlling the incubation time, temperature and volume of diluent. The suspension is then used to inoculate a container containing the broth compound. The container is then incubated at the appropriate temperature, after incubation the container is inspected for growth / non-growth. Minimum inhibitory concentration (M
IC) is defined as the lowest concentration of compound that gives the result of complete inhibition of the growth of the test organism.

The organisms tested to show biocidal activity are: Bacteria Pseudomonas aerugin
osa: Psae), Gram-negative; Escherichia coli (Esc)
herichia coli: Ecol), Gram-negative; Staphylococcus aureus: Sau
r), Gram positive; Fungus Aspergillus niger (Ani)
g); Aureobasidi pullulans
um pullulans: Apul); Chlorella pyroidenosa (Ch)
lor).

Table 2: Biocidal Evaluation Results of Minimum Inhibitory Concentration (MIC) Test MIC (ppm) Compound Psae Ecol Saur Anig Apul Chlor 1> 250> 250> 250 8 4 <0.12 2> 250> 250 2 2 1> 250 3 250> 250 125 2 8-4> 250> 250 32 250 16-5> 250> 250 250 1 0.25 8 6> 250> 250 250 125 63> 250 7> 250> 250> 250 63 8-8> 250> 250 32 <0.12 <0.12 32 9> 250> 250 63 1 1 4 10> 250> 250 125 16 125 125 11> 250> 250 32 1 0.25 8 12> 250> 250 32 125 250 250 13> 250> 250 <0.12 1 32-14> 250> 250> 250 <0.12 <0.12-15 125> 250 32 1 <0.12-

Example 4 Evaluation of Agronomic Bactericidal Activity of Compound The compound of the present invention was treated with rice leaf blight (rise blas).
t: RB), tomato leaf spot (tomato late)
bright: TLB, wheat powdery mildew (white)
powdery mildew (WPM), botrytis on tomato
o: BOT), cucumber anthracnose (cucumber a)
nthracnose (CA), rice helmintsporium
m: RH), wheat groom blotch (white gl)
ume blot: SNW) and wheat rust (wh
It was tested for in vivo bactericidal activity against the eat leaf trust (WLR). The results are shown in Table 3.
In grain studies (except for rice seedlings used to test rice leaf blight), about 2 of the application of fungicidal compounds was used.
Plants were trimmed 4 hours before to give a uniform seedling height and to facilitate uniform application of the compound and inoculation of the fungus. The compounds were dissolved in a 2: 1: 1 mixture of water, acetone and methanol, sprayed onto the seedlings, dried (4-6 hours) and then the seedlings were inoculated with the fungus.
In each test, a control seedling sprayed with a mixture of water, acetone and methanol and inoculated with the fungus was used. The remaining techniques for each trial were as follows, the results were a disease-controlled percentage (no development or signs of disease in seedlings treated with the compounds of the invention compared to untreated control seedlings). The ratio of things).

Rice Leaf Blight (RB) Pyricularia oryzae was sprayed on seedlings of Natto rice by spraying the leaves and stems with an airbrush until a uniform film of inoculum was observed on the leaves. Was inoculated (about 20,000 conidia / ml). Incubate the inoculated seedlings in a humidified atmosphere (75 ° F-85 ° F) for about 24 hours and then in a greenhouse atmosphere (70 ° F-75 ° F).
F). The rate of disease control was measured 7-8 days after inoculation.

Tomato Leaf Spot (TLB) In a controlled atmosphere room (65 ° F to 70 ° C).
F, relative humidity 100%), 4 weeks old Pixie (Pixi
e) Phytophthora infestans on tomato seedlings
Were cultured. After storage, wash the spores from the leaves with water,
A DeVilbiss atomizer was used to disperse the bactericide to be tested on the seedlings of Pixie tomato of 3 weeks old which had been sprayed in advance. To infect, the inoculated seedlings were placed in a humidified container kept at 70 ° F and constant mist for 24 hours. The seedlings were then transferred to a controlled atmosphere container similar to that described above and incubated for a further 3 days before evaluation. Disease control levels were recorded as percentage of control 4 days after inoculation and 5 days after compound spraying.

Wheat powdery mildew (WPM) 65 on Pennol wheat seedlings
Erysiphe graminis in a controlled temperature room from ° F to 75 ° F
s (f.sp. tritici)) was cultured. Powdery mildew spores were shaken from the cultured seedlings onto pennol wheat seedlings that had been pre-sprayed with the fungicide compound. The inoculated seedlings are kept in a room at a controlled temperature of 65 ° F to 75 ° F and submerged (subirrig).
ate). Disease control rates were evaluated 8-10 days after inoculation.

Wheat Rust (WLR) 7 days old wheat (cultivator fielder (cult)
on ivar Fielder))
Reconditioner (puccinia recondit)
a) (f.sp. tritici Races PKB and PLD) were cultured for 14 days in the greenhouse. By cyclone vacuum,
Alternatively, spores were collected from the leaves by sedimentation on aluminum foil. The spores were washed by sieving through a screen with a 250 micron opening and stored or used fresh. Save to Ultralo
A sealed bag in a w freezer was used. If it is stepped, the spores must be heat shocked at 40 ° F for 2 minutes before use. Spore suspension, Soltr
Prepared from dried spores by adding 20 mg (9.5 million) per ml of ol oil. The suspension was distributed in gelatin capsules (volume 0.7 ml) and attached to an oil atomizer. Fielder Wheat 2 of 7 days
One capsule was used per 20 sides of an inch square pot. After waiting at least 15 minutes for the oil to evaporate from the wheat leaves, the seedlings were placed in a humid dark room (dark mi).
st chamber) (18 to 20 ° C, relative humidity 10)
0%). The seedlings were then placed in the greenhouse for a latent period and evaluated for disease levels after 10 days.
Protective and therapeutic tests were carried out 1 day and 2 days after inoculation, respectively, before spraying the test chemicals on the seedlings.

Botrytis on tomato (BOT) Botrytis cinerea (botrytis ci) used
Toxicity was confirmed by inoculating the seeds of N. In the test, spore suspensions from at least two species were prepared and mixed in equal volumes. All media were kept on PDA (potato dextrose agar) and incubated for 2-3 weeks at room temperature and room light in a sealed plastic box before use in the test.

The inoculum was prepared as follows. A dextrose solution in tap water (1.9 g / 100 ml) was prepared and poured onto each culture plate of sporulated bacteria. Plate the rubber policeman (rubber
rubbed with a policeman),
The solution was filtered through two layers of cotton cloth. 5 to 6.5 x 10
A spore suspension of ⁵ spores / ml is preferred. Pixie tomato seedlings having a height of about 8 to 10 cm at the age of 3 to 4 weeks were placed on an indirect head house (hea) before use (inoculation).
Place in light) for at least 2 days. Seedlings were inoculated by spraying with a DeVilbiss atomizer onto the surface of the upper and lower leaves of the seedlings and the stem until just before dripping. Seedlings at 70 ° F and humidity of 10
Stored in indirect room light on 0% mist bench and evaluated for results 5-7 days.

Cucumber anthracnose
tracnose (CA) Colletotrichum lagenarium (Coletotr)
Ichum lagenarium) under dark conditions,
Potato dextrose agar (PD
Cultured on A) for 14 days. Plates were inoculated by spreading the inoculum on the medium with an inoculating needle. Spores were then harvested from the plates by adding deionized water to the PDA plates. After rubbing the surface of the agar with a rubber policeman and filtering the spore suspension through a cotton cloth to remove mycelia and agar fragments, 1-2
The concentration was adjusted to 10 ⁵ spores / ml.

Cucumber seedlings (var Marker, 14 days old) were inoculated by spraying the leaves (especially on the underside) until a uniform film of the inoculum was observed on the seedlings. .. The inoculated seedlings were then incubated for 24 hours at 70-75 ° F in a humid atmosphere, then removed, dried and placed under greenhouse conditions. A comparison of treatments was made 10-14 days post inoculation.

Rice helmintosporium (RH) Bacteria were grown on PDA under artificial light. Decree 3
Spores from week to March were used. Fill the plate with DI water,
Scrape with a spatula and filter the wash through a layer of cotton cloth.

Using a DeVilbis air inoculator, 2
Inoculation was performed by applying 100,000-500,000 spores per side of 0 seedlings. After incubating the seedlings in a humidity container at 25 ° C. for 24 hours,
Placed under greenhouse conditions and evaluated after 6 days.

Wheat Groom Blotch
ume blot (SNW) Septoria nodrum (stage of ascomycetes, Leptosphaeria nodrum)
aerial nodrum)) a portion of the inoculum from a 2-3 week old colony of Czapek-DoxV-8.
Incubation was carried out on an agar plate in the dark, alternating between light and dark conditions (12 hours / 12 hours) at 20 ° C. for 48-72 hours.

Deionized water (1 per 10-15 plates)
00ml) to a 1/2 gallon jar, then 10
A spore solution for inoculation was prepared by transferring the fungal material from 20 culture plates to a jar. 15 jars
Shake vigorously for 30 seconds and let stand for 5-10 minutes. The spore concentrate was then filtered through a cotton cloth and diluted to the appropriate concentration (suitably 3.0 x 10 ⁶ spores / ml). 30 ~
Forty plates yielded about 1 liter of diluted inoculum. One week old Fielder (untreated seed) wheat seedlings were used for disease evaluation. About 22 ml of inoculum was added to DeVil
Wheat seedlings (inside 20 pots) were applied using a biss atomizer. After air-drying the surface for 10 to 15 minutes, it was stored in a humidity container at 20 ° C., light / dark = 12 hours / 12 hours, and humidity 100%. After incubating the seedlings for 96 hours, they were transferred to an atmosphere container and allowed to develop disease for 8 days before being evaluated for results.

Table 3 Greenhouse test results for disease control of seedlings Compound rating (Rate) BOT CA RB RH SNW TLB WLR WPM 1 200 75 75 0 99 50 0 0 0 2 200 75 50 0 90 50 0 0 0 3 200 90 85 0 95 0 0 50 25 4 200 0 85 0 95 50 0 50 0 5 200 0 85 0 95 50 0 0 0 6 200 75 50 0 90 0 0 0 0 7 200 50 75 0 99 0 0 0 0 8 200 75 75 50 99 50 0 90 0 9 200-75 0 95 50 0 80 0 10 200 90 80 0 95 50 0 50 0 11 200 75-50 99 0 0 0 0 12 200 75 75 50 95 0 0 0 0 13 200 75 85 50 95 50 90 90 0 14 200 50 90 50 95 80 90 90 0 15 200 90 90 80 95 50 80 80 0

Although the present invention has been described in terms of particular embodiments and applications, other modifications and uses of the invention will occur to those skilled in the art without departing from the spirit and scope of the invention as defined in the claims. it is obvious.

Claims (18)

[Claims] 1. The following formula: (Wherein A is selected from the group consisting of hydrogen, alkyl, aryl and heterocyclic groups; R is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted Or unsubstituted phenyl and a substituted or unsubstituted heterocyclic group; X is selected from the group consisting of halogen). 2. A is hydrogen; C₁  ~ C₁₈ Straight or branched
Alkyl; C₃  ~ C₈  Cycloalkyl; C₃  ~ C₆  Al
Kenyl; C₃  ~ C_Five  Alkynyl; C₇  ~ C₁₂Aralchi
Le; C₆  ~ C₁₂ Aryl; halogen, C₁  ~ C_Four  Archi
Le, C₁  ~ C_FourAlkoxy, nitro, cyano, carboxy
Sill, C₁  ~ C_Four  Alkoxycarbonyl, C₁  ~ C_Four  A
Luquilcio,- S (O)_n  R₂(Where n is 1 or 2
And R2 Is C1 ~ C4 Which is alkyl)
C6 substituted with 1 to 3 substituents selected from
~ C12 Aryl; and halo-substituted, nitro-substituted or non-substituted
Substituted 2-thienyl, 3-thienyl, 2-furyl, 3-furan
Ryl, 2-pyridyl, 3-pyridyl and 4-pyridyl
A group selected from the group consisting of;
The compound according to claim 1, which is a compound. 3. A is hydrogen, 4-chlorophenyl, 3-
Chlorophenyl, 2-methylphenyl, 4-methylphenyl, 3-methylphenyl, 2-thienyl, 2-nitrophenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 3- Methoxyphenyl, 4-bromophenyl, 2
-Fluorophenyl, 2-chloro-4-nitrophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, methyl, iodopropargyl, t-butyl, phenyl, 4-nitrophenyl, It is selected from the group consisting of 3-fluorophenyl, 1-naphthyl, 2-naphthyl, 3-pyridyl, 3-bromophenyl, 3-ethoxyphenyl, n-propyl, 2-chlorophenyl, cyclohexyl and 2-furyl. The compound according to claim 1. 4. The compound according to claim 1, wherein X is I. 5. R is methyl, ethyl, isopropyl,
n-butyl, phenyl, 4-chlorophenyl, allyl,
The compound according to claim 1, which is selected from the group consisting of 2-propynyl, 2-furyl, 2-thienyl, 3-iodo-2-propynyl, 3-nitrophenyl, 3-methoxyphenyl and 4-methylphenyl. .. 6. R is hydrogen; C₁ ~ C₁₈Straight or branched
Alkyl; C₃ ~ C₈ Cycloalkyl; C₃ ~ C₆ Al
Kenyl; C₃ ~ C_Five Alkynyl; C₇ ~ C₁₂Aralchi
Le; C₆ ~ C₁₂Aryl; halogen, C₁ ~ C_Four Archi
Le, C₁ ~ C_Four Alkoxy, nitro, cyano, carboxy
Sill, C₁ ~ C_Four Alkoxycarbonyl, C₁ ~ C_Four A
Rukiruthio, -S (O)_n R² (Where n is 1 or 2
Yes, R² Is C₁ ~ C_Four A group consisting of)
C substituted with 1 to 3 substituents selected from₆ ~
C₁₂Aryl; and halo-substituted, nitro-substituted or unsubstituted
2-thienyl, 3-thienyl, 2-furyl, 3-free
Selected from the group consisting of 2-pyridyl, 3-pyridyl
A group selected from the group consisting of:
The described compound. 7. A composition comprising a compound according to claim 1 and an agriculturally acceptable carrier. 8. A composition comprising the compound according to claim 1 and a cosmetic agent. 9. A composition comprising the compound of claim 1 and a cutting oil. 10. A composition comprising the compound of claim 1 and a soap or synthetic detergent. 11. A composition comprising the compound of claim 1 and a stabilizer. 12. A composition comprising the compound according to claim 1 and a film-forming material. 13. The following formula: The method for producing a compound according to claim 1, which comprises reacting the compound of claim 1 with an iodizing agent or a brominating agent. 14. A method comprising controlling a microorganism using the compound of claim 1. 15. A method comprising controlling a fungus with the compound of claim 1. 16. A method comprising controlling a bacterium with the compound of claim 1. 17. A method comprising controlling algae, viruses or yeast with the compound of claim 1. 18. Wood, paints, adhesives, glues, papers, cloths, leathers, plastics, cardboards, lubricants, cosmetics, foods, caulks, feeds and industries using the composition containing the compound of claim 1. A method comprising protecting cooling water for microorganisms.