JP2597848B2 - Industrial fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel industrial germicides.

The present inventors have investigated various novel fungicidal compounds and found that the general formula (Wherein R is an alkyl group, nitro group, chlorine atom, bromine atom or iodine atom, X is chlorine atom or bromine atom, m and n
Represents a number of 1 or 2, provided that when R is an alkyl group, m
Is 2) was found to be an industrially excellent fungicide.

The present inventors have performed a basic potency test on microorganisms to allow the compounds of formula I to be gram-positive, gram-negative,
It has been found that they exhibit an excellent bactericidal effect on microorganisms such as yeasts and molds. Furthermore, as a result of conducting tests based on actual conditions for various industrial uses, it was found that the compound of the formula I was found to be a preservative for papermaking slime, a preservative for fiber oils, a preservative for cutting oils, a latex, a coating color, casein, lignin and the like. It has been found to be industrially valuable as an agent, an antifungal agent such as starch paste, paint, adhesive, and a pulp antifungal agent.

Compounds of formula I have the general formula Wherein R has the meaning described above,
It is obtained by chlorination or bromination in a solvent. As the solvent, a chlorinated solvent such as chloroform, carbon tetrachloride, alcohol, and glycol are used. For chlorination, a chlorinating agent such as chlorine gas or sulfuryl chloride can be used. For bromination, a brominating agent such as bromine or N-bromosuccinimide can be used.

Examples of the compound of the formula I include the following compounds. 2-bromo-1- (5-chloro-2-thienyl) ethanone (compound 1, melting point 71-72 ° C.), 2,2-dibromo-
1- (5-chloro-2-thienyl) ethanone (compound 2, melting point 44.5-46 ° C.), 2-bromo-1- (5-bromo-2-thienyl) ethanone (compound 3, melting point 92-93)
° C), 2,2-dibromo-1- (5-bromo-2-thienyl) ethanone (compound 4, melting point 45-46 ° C), 2-bromo-1- (5-iodo-2-thienyl) ethanone (compound 5, melting point 104-105 ° C), 2-bromo-1- (5-nitro-2-thienyl) ethanone (compound 6, melting point 78-79)
° C), 2-bromo-1- (2,5-dimethyl-3-thienyl) ethanone (compound 7), 2,2-dibromo-1- (2,5
-Dimethyl-3-thienyl) ethanone (compound 8) and the like.

The industrial bactericide of the present invention can be usually used by mixing the compound of the formula I with a carrier or a solvent and formulating it into a liquid, emulsifier, suspension, wettable powder or the like using an auxiliary in some cases. .

Examples of the solvent include alcohols such as methanol, ethanol and propanol, ethylene glycol, polyethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, glycols such as cellosolves, aromatic solvents such as beyzen, toluene and xylene, ligroin, kerosene, and light oil. And petroleum solvents such as spindle oil and naphtha oil, esters such as ethyl acetate and butyl acetate, dioxane, dimethylformamide, and dimethyl sulfoxide. As the inorganic carrier, kaolin, talc, calcium carbonate, zeolite, sodium sulfate, magnesium sulfate and the like are used. As the auxiliary agent, for example, anionic, nonionic, cationic surfactants, pastes and the like are used.

Industrial disinfectant of the present invention, fibrous oils, cutting oils, latex, coating color, casein, lignin, starch paste, paints, adhesives, etc., 0.1 to 100 as an active ingredient
It is preferable to add at a rate of 0 ppm.

Formulation Example 1 (liquid preparation) 2-bromo-1- (5-chloro-2-thienyl) ethanone 20 parts Diethylene glycol monomethyl ether 80 parts The above components were mixed and dissolved to obtain a 20% liquid preparation.

Formulation Example 2 (solution) 20 parts of 2-bromo-1- (5-iodo-2-thienyl) ethanone 80 parts of dimethylformamide The above components were mixed and dissolved to obtain a 20% solution.

Formulation Example 3 (suspension) 2-bromo-1- (5-nitro-2-thienyl) ethanone 20 parts Xanthan gum 0.5 parts Demol N (Kao Corporation anionic surfactant) 0.5 parts Water 79 parts Mix the above ingredients To give a 20% suspension.

Example 1 A basic antibacterial activity test of a compound of formula I was performed. The test bacteria include Micrococcus haogenes pearl aureus (MP), Bacillus subtilis (BS), Escherichia coli (EC), and Aerobacter aerogenes (A.
a), Pseudomonas aeruginosa (Pa), Aspergillus niger (An), Penicillium citrinum (Pc), Trichoderma T-1 (TT-1), Trichoprosis kyandida (Tc) and Geotricum candidium (Gc) Was. The test method used was an agar plate dilution method. The cultivation conditions were waxman's medium for bacteria,
Cultured at 35 ° C for 48 hours, yeasts and molds were Tuapec medium, 28
° C, 7 days. The results are shown in Table 1-A and Table 1-B.

Example 2 A slime collected from a stoichinet in a papermaking process centered on a corrugated cardboard was pre-cultured in a Waxman liquid medium to obtain a test bacterial solution. 50m sterile water in a 100ml shake flask
l, put Waxman liquid medium 10ml and test bacterial solution 1ml,
The compound of the formula I was added to the culture solution at 1, 5, and 10 ppm, and cultured with shaking at 37 ° C. 660nm of this culture
Was measured over time to determine the effect of inhibiting the proliferation of slime-forming bacteria. Table 2 shows the results. The suppression time in the table is the time until the absorbance of each culture solution becomes 0.1, and the stronger the effect, the longer the suppression time.

Example 3 Rapeseed oil 30 parts, liquid paraffin 10 parts, beef tallow 15 parts, lauryl alcohol sulfate 15 parts, Nissan Nonion O-
4 and O-15 (nonionic surfactant, manufactured by Nippon Oil & Fats Co., Ltd.) A fibrous oil agent consisting of 5 parts of each was diluted 20 times with water so that the compound of formula I became 50 and 100 ppm with respect to the diluent. Was added. Put the putrefactive oil collected from the textile factory into 5
The mixture was shaken in a thermostat at 37 ° C. for 8 hours a day.
After 4 days and 7 days, the presence or absence of spoilage and the viable cell count were examined. Table 3 shows the results.

Example 4 A corn starch 10% solution was gelatinized by heating at 90 ° C. for 30 minutes, and after cooling, the compound of the formula I was added to the paste solution at 100 and 200 ppm.
And mixed well. 0.1 g each of the size liquid was applied to the front and back of a filter paper having a diameter of 3 cm, and was naturally dried to obtain a test piece. After spraying 0.1 ml of the mixed spore suspension on the surface of the agar medium in a 90 mm diameter dish, place one test piece in the center, and further spray 0.05 ml of the spore suspension uniformly on the test piece.
The lid was covered and cultured in an incubator at 28 ° C. for 14 days, the mold was observed on the test piece, and the mold resistance was determined. Table 4 shows the results. As mixed spores, spores of Aspergillus niger pericillium citrinum and Cladosporium cladopolioides were used.

Agar medium composition Ammonium nitrate 3.0 g Monopotassium phosphate 1.0 g Magnesium sulfate 0.5 g Potassium chloride 0.25 g Ferrous sulfate 0.002 g Agar 25 g Water 1000 ml Mold resistance test criterion 3: No hyphal growth was observed in the inoculated portion of the test piece.

2: The area of the hyphal growth part observed in the inoculated part of the test piece does not exceed 1/3 of the total area.

1: The area of the hyphal growth part observed in the inoculated part of the test piece exceeds 1/3 of the total area.

Claims (1)

(57) [Claims] (1) General formula (Wherein R is an alkyl group, nitro group, chlorine atom, bromine atom or iodine atom, X is chlorine atom or bromine atom, m and n
Represents a number of 1 or 2, provided that when R is an alkyl group, m
Is an industrial bactericide, which comprises a compound represented by the formula (2):