JPH026721B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antibacterial, antifungal, and herbicide containing a certain type of terpene acetate compound as an active ingredient. In recent years, it has been used for industrial and pharmaceutical purposes, which are inexpensive and have excellent effects.
Antibacterial and antifungal agents for agricultural use are in demand. In order to deeply search for compounds that are effective for such purposes, the present inventors have synthesized and tested a large number of derivatives using a monoterpene compound having 10 carbon atoms, which is an inexpensive industrial raw material, as a starting material. Among these derivatives, the C ₁₀ monoterpene ester compound of halogenoacetic acid was found to exhibit particularly excellent antibacterial activity against iatrogenic fungi, wood-decaying fungi, and slime-constituting microorganisms, and also has herbicidal activity. Therefore, the present invention provides an antibacterial, antifungal, and herbicide agent containing a compound represented by the formula XCH ₂ COOR () (wherein X represents a halogen atom and R represents a monoterpene group) as an active ingredient. It is something to do. In formula (), X is preferably a chlorine, bromine or iodine atom, and preferred examples of the monoterpene group represented by R are a bornyl group, an isobornyl group, a menthyl group, a tetrahydroperylyl group, a perylyl group and a terpinyl group. . The active ingredient compound of the present invention represented by formula () can be produced according to known methods, such as a dehydration reaction between a halogenoacetic acid and a monoterpene alcohol, or a reaction between a halogenoacetic acid and a monoterpene compound having a double bond. It can be produced by addition reaction, halogen exchange reaction of halogenoacetate, etc. Representative examples of the compound represented by formula () include the following compounds. Bornyl bromoacetate, Bornyl iodoacetate, Bornyl chloroacetate, Bornyl trichloroacetate, Isobornyl iodoacetate, Isobornyl bromoacetate, Isobornyl chloroacetate, Isobornyl trichloroacetate, Menthyl iodoacetate, Menthyl chloroacetate , tetrahydroperylyl iodoacetate, tetrahydroperylyl chloroacetate, tetrahydroperylyl bromoacetate, α-terpinyl iodoacetate, α-terpinyl chloroacetate, perilyl iodoacetate, perilyl bromoacetate. The active ingredient compound of the present invention represented by the formula () is useful as an antibacterial and antifungal agent, and exhibits a strong growth-disturbing effect on a wide range of bacteria and fungi. It is useful in the fields of household medicine, agriculture, and industry to improve unfavorable symptoms and conditions caused by the growth of bacteria and fungi. That is, for medical use, for example, 0.1 to 5% as an active ingredient in liquids and ointments for the treatment of external diseases caused by fungi such as Candida, Aspergillus, Trichophyton, and Cryptococcus.
It is preferably blended in a range of 0.5 to 2% and applied to the affected area to achieve the therapeutic purpose. Furthermore, it can also be used as a sterilizer or disinfectant for other medical purposes or for animals such as pets and household animals to prevent the growth of pathogenic bacteria and fungi, or to treat external diseases caused by the growth of these bacteria. Furthermore, the active ingredient compound of the present invention also shows usefulness in the agricultural and industrial fields. In particular, in these fields, agricultural and industrial products such as seeds, seedlings, wood, agricultural and horticultural crops, woodwork, pure crafts, leather, fibers, adhesives, paints, pulp, circulating water for cooling, synthetic resins, and The occurrence of putrefactive bacteria and mold in the manufacturing environment causes a serious loss in the value of the product. Since the active ingredient compound of the present invention exhibits a growth inhibiting effect on harmful bacteria and fungi in these agricultural and industrial fields, it can be used for the purpose of maintaining the quality of products in these fields and preserving the environment. . Furthermore, the active ingredient compound of the present invention represented by formula () was found to have very good and very broad-spectrum herbicidal activity against a large number of annual and perennial monocotyledonous and dicotyledonous weeds.
This broad-spectrum herbicidal action, usually associated with a wide variety of weeds, can be used, for example, to control undesirable plants growing in non-agricultural areas such as roadsides, building sites, etc., or to control undesirable aquatic plants. It is effective for These compounds also
It can also be used to control weeds in orchards, etc., and can also be used to control weeds in annual crops if it is applied before sowing, before germination, or after harvesting of cultivated plants. In the agricultural and industrial fields, the active ingredient compound of the present invention can be used as an antibacterial, antifungal, and herbicide formulation, either as it is or in preparations held on commonly used carriers, such as oil solvents, emulsions, pastes,
Examples include powders, wettable powders, aerosols, antifungal paints, and adhesives. Examples of carriers used include inorganic solid carriers such as clay, talc, bentonite, kaolin, silicic anhydride, and calcium carbonate, organic solvent carriers such as kerosene, ligroin, xylene, dimethylformamide, and dimethyl sulfoxide, and dimethyl ether and chlorofluorocarbon gas. Gas carriers are mentioned;
Auxiliary agents to further enhance the effectiveness of formulations include ionic and nonionic surfactants and polymeric compounds such as polyvinyl acetate and methyl cellulose, as well as other antiseptic and antifungal agents such as thiabendazole. It is also possible to use it in combination with pesticides, insecticides, fungicides, and herbicides. The content of the active ingredient compound of the present invention in the formulation can vary widely depending on the formulation, but is generally from 0.01 to 95% by weight, preferably from 0.2 to 95% by weight.
A range of 40% by weight is suitable. Next, test examples will be shown to illustrate the effects of the antibacterial, antifungal, and herbicide of the present invention. The test compound was produced as follows. Compound No. 1: Isobornyl chloroacetate Camphene 200g, Monochloroacetic acid 143g, n
- Add 2.3 g of sulfuric acid to 100 ml of hexane solution,
The reaction was carried out at ~50°C for 6 hours. Add the reaction solution to water,
Washed with sodium carbonate aqueous solution and water sequentially, n-
Hexane was distilled off to obtain 328 g of the desired oily inbornyl chloroacetate. Mass spectrum (EI) 230 (M ⁺ ) Compound No. 2: Isobornyl iodoacetate 200 g of potassium iodide was added to a solution of 230 g of isobornyl chloroacetate and 250 g of acetone, and the mixture was refluxed for 4 hours. After distilling off the acetone, 200 g of toluene was added, the mixture was washed with water, and the toluene was distilled off to obtain 315 g (yield: 97%) of the desired oily substance of isobornyl iodoacetate. Mass spectrum (EI) 322 (M ⁺ ) Compound No. 3: Isobornyl bromoacetate Camphene 136g, Monobromoacetic acid 153g, n
- Add 2 g of sulfuric acid to a solution of 200 g of hexane,
The reaction was carried out at ~50°C for 5 hours. Treated in the same manner as for Compound No. 1 to obtain 248 g of the desired oily substance of isobornyl bromoacetate (yield 90%).
I got it. Mass spectrum (EI), 274 (M ⁺ ) 276 (M ⁺ +2) Compound No. 4: Isobornyl trichloroacetate Camphene 136 g, Trichloroacetic acid 180 g, n
- 2 g of sulfuric acid was added to a solution of 200 g of hexane, and the reaction was carried out at room temperature for 5 hours. Treated in the same manner as for compound No. 1 to obtain 272 g of the desired oily substance of isobornyl trichloroacetate (yield 91%).
I got it. Mass spectrum (EI) 298 (M ⁺ ) Compound No. 5: Tetrahydroperylyl chloroacetate A solution of 152 g of tetrahydroperillyl alcohol, 110 g of monochloroacetic acid, and 300 g of toluene was azeotropically dehydrated. After the reaction, the mixture was treated in the same manner as for Compound No. 1 to obtain 218 g (yield: 95%) of the desired oily product of tetrahydroperylyl iodoacetate. Mass spectrum (EI) 232 (M ⁺ ) Compound No. 6: Tetrahydroperylyl iodoacetate Tetrahydroperylyl chloroacetate 115
A solution of 200 g of acetone, 200 g of potassium iodide, and 92 g of potassium iodide was reacted and treated in the same manner as for compound No. 2 to obtain 148 g (yield: 93%) of the desired oily product of tetrahydroperylyl iodoacetate. Mass spectrum (EI) 324 (M ⁺ ) Compound No. 7: Tetrahydroperylyl bromoacetate A solution of 154 g of tetrahydroperillyl alcohol, 153 g of monobromoacetic acid, and 300 g of toluene was azeotropically dehydrated. After the reaction, the reaction mixture was treated in the same manner as for Compound No. 1 to obtain 246 g (yield: 93%) of the desired oily product of tetrahydroperylyl bromoacetate. Mass spectrum (EI) 276 (M ⁺ ), 278 (M ⁺ +2) Compound No. 8: α-terpinyl chloroacetate β-pinene 41 g, monochloroacetic acid 29 g, water
5.4g of the solution was reacted at 60°C for 6 hours. After the reaction, 100 g of n-hexane was added and treated in the same manner as for compound No. 1 to obtain 15 g of the desired oily product of α-terpinyl chloroacetate. Mass spectrum (EI) 230 (M ⁺ ) Compound No. 9: α-terpinyl iodoacetate A solution of 15 g of α-terpinyl chloroacetate, 35 g of potassium iodide, and 100 g of acetone was prepared in the same manner as for compound No. 2. React and process target α-terpinyl iodoacetate oil 20
I got g. Mass spectrum (EI) 322 (M ⁺ ) Compound No. 10: Menthyl chloroacetate Menthol 152g, chloroacetic acid ester 110
g, p-toluenesulfonic acid 2g, toluene
300 g of the solution was refluxed for 5 hours with dehydration.
After the reaction, the desired oily substance of menthyl chloroacetate is obtained by processing in the same manner as in the case of compound No. 1.
Obtained 217g. Mass spectrum (EI) 232 (M ⁺ ) Compound No. 11: Menthyl iodoacetate A solution of 115 g of menthyl chloroacetate, 92 g of potassium iodide, and 200 g of acetone was mixed with Compound No. 11: Menthyl iodoacetate.
The reaction and treatment were carried out in the same manner as in case 2 to obtain 147 g of the desired menthyl iodoacetate oil. Mass Spectrum (EI) 324 (M ⁺ ) Test Example 1 The antifungal activity of the test compound was measured using a conventional method on a numerical test bacterium (iatrogen strain). The results are shown in Table 1 as minimum inhibitory concentration (mcg/ml).

[Table] Test example 2 Antibacterial activity test against plant pathogenic bacteria.
An agar plate dilution medium containing 100 ppm was prepared, and test bacteria were smeared and inoculated thereto, and cultured at 25°C for 3 days. Antibacterial activity was determined by determining the growth state on a medium containing no drug, with a score of - indicating no growth at all, and a grade of + in between depending on the degree of growth.

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[Table] Pear black spot fungus

[Table] Rice sheath blight fungus test example 3 Antibacterial activity test against industrial material harmful bacteria Tested in the same manner as in Test Example 2 using the industrial material harmful bacteria listed in Table 4 as test bacteria, and after culturing for 10 days. The growth level of the test bacteria was determined in the same manner as in Test Example 2.

[Table] Test Example 4 Herbicidal Activity Test A porcelain pot with a diameter of 9 cm was filled with field soil, and the following crop and weed seeds were sown and lightly covered with soil. After sowing, the plants were grown in a greenhouse (daytime: 25°C, night: 20°C). Chemical treatment was carried out the day after sowing in the soil treatment test, and 10 days after sowing in the foliage treatment test. Evaluation of drug efficacy was carried out on the 7th and 10th day after drug treatment using the following 6-level index evaluation method. Symbols in Tables 5 and 6 of test plants Japanese daisy A Japanese radish B Japanese barnyard grass C Corn D Rice E Wheat F Japanese crabgrass G Japanese chrysanthemum H Medicinal efficacy index 0 Harmless 1 20% killing effect 2 40% 〃 3 60% 〃 4 80% 〃 5 Complete death

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Claims (1)

[Scope of Claims] 1. An antibacterial, antifungal, and herbicide containing a compound represented by the formula XCH ₂ COOR (wherein, X represents a halogen atom and R represents a monoterpene group) as an active ingredient. 2. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is bornyl iodoacetate. 3. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is bornyl bromoacetate. 4. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is bornyl chloroacetate. 5. The antibacterial and antifungal agent according to claim 1, wherein the active ingredient is isobornyl iodoacetate.
Herbicide. 6. The antibacterial and antifungal agent according to claim 1, wherein the active ingredient is isobornyl bromoacetate.
Herbicide. 7. The antibacterial and antifungal agent according to claim 1, wherein the active ingredient is isobornyl chloroacetate;
Herbicide. 8. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is isobornyl trichloroacetate. 9. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is menthyl iodoacetate. 10. The antibacterial, antifungal, herbicide according to claim 1, wherein the active ingredient is menthyl chloroacetate. 11. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is tetrahydroperylyl chloroacetate. 12. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is tetrahydroperylyl iodoacetate. 13. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is tetrahydroperylyl bromoacetate. 14. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is bornyl trichloroacetate. 15. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is α-terpinyl iodoacetate. 16. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is α-terpinyl chloroacetate. 17. The antibacterial, antifungal, and herbicide according to claim 1, wherein the active ingredient is perilyl iodoacetate. 18. The antibacterial, antifungal, herbicide according to claim 1, wherein the active ingredient is perylyl bromoacetate.