JPS632419B2 - - Google Patents

Description

[Detailed description of the invention]

This invention is based on the general formula (In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a phenyl group with or without 1 to 3 substituents selected from a halogen atom, a lower alkyl group, and a lower alkoxy group) The present invention relates to a trihaloallyl derivative having the same as an active ingredient, and a termiticide, a fungicide, and a preservative containing the trihaloallyl derivative as an active ingredient. In the general formula (), X preferably represents an iodine or bromine atom. R is preferably phenyl, o
-, m- or p-chloro (or bromo) phenyl, 2,3-,2,4-,2,5-,2,6
-,3,4- or 3,5-dichlorophenyl, 2,3,5- or 2,4,6-trichlorophenyl, o-, m- or p-methylphenyl, p-ethylphenyl, 2,3- ,2,4
-, 2, 5-, 2, 6-, 3, 4- or 3,
5-dimethylphenyl, 2,3,5-,2,4,
6-trimethylphenyl, o-, m- or p
-methoxyphenyl, 2,3- or 2,6-
Halogen atoms such as dimethoxyphenyl, 4-chloro-2-methylphenyl, 4-chloro-3-methylphenyl or 2-chloro-5-methoxyphenyl, C _1-4 alkyl groups especially methyl and/
or a C _1-4 alkoxy group, particularly a phenyl group with or without 1 to 3 methoxy as a substituent. Among the compounds having the above general formula (), those which are particularly effective for the purpose of the present invention are those in which X is iodine and R is halogen or methyl, m- or p-
It is a phenyl group with or without one substituent at the position. Examples of compounds having the general formula () of the present invention are as follows. (The compound number is referred to in the following description.) 1 3-phenoxy-1,1,2-triiodo-
1-Propene2 3-(o-chlorophenoxy)-1,1,2-
Triiodo-1-propene 3 3-(m-chlorophenoxy)-1,1,2-
Triiodo-1-propene 4 3-(p-chlorophenoxy)-1,1,2-
Triiodo-1-propene 5 3-(2,4-dichlorophenoxy)-1,
1,2-triiodo-1-propene 6 3-(2,3-dichlorophenoxy)-1,
1,2-triiodo-1-propene 7 3-(2,5-dichlorophenoxy)-1,
1,2-triiodo-1-propene8 3-(2,6-dichlorophenoxy)-1,
1,2-triiodo-1-propene 9 3-(3,4-dichlorophenoxy)-1,
1,2-triiodo-1-propene10 3-(2,4,5-trichlorophenoxy)-
1,1,2-triiodo-1-propene11 3-(o-methylphenoxy)-1,1,2-
Triiodo-1-propene12 3-(m-methylphenoxy)-1,1,2-
Triiodo-1-propene13 3-(p-methylphenoxy)-1,1,2-
Triiodo-1-propene14 3-(p-ethylphenoxy)-1,1,2-
Triiodo-1-propene 15 3-(2,4-dimethylphenoxy)-1,
1,2-triiodo-1-propene16 3-(2,5-dimethylphenoxy)-1,
1,2-triiodo-1-propene17 3-(3,4-dimethylphenoxy)-1,
1,2-triiodo-1-propene18 3-(2,3,6-trimethylphenoxy)-
1,1,2-triiodo-1-propene19 3-(o-bromophenoxy)-1,1,2-
Triiodo-1-propene20 3-(m-bromophenoxy)-1,1,2-
Triiodo-1-propene21 3-(p-bromophenoxy)-1,1,2-
Triiodo-1-propene22 3-(o-methoxyphenoxy)-1,1,2
-triiodo-1-propene23 3-(m-methoxyphenoxy)-1,1,2
-triiodo-1-propene24 3-(p-methoxyphenoxy)-1,1,2
-triiodo-1-propene25 3-(2,3-dimethoxyphenoxy)-1,
1,2-triiodo-1-propene26 3-(2,6-dimethoxyphenoxy)-1,
1,2-triiodo-1-propene27 3-(4-chloro-2-methylphenoxy)-
1,1,2-triiodo-1-propene28 3-(4-chloro-3-methylphenoxy)-
1,1,2-triiodo-1-propene29 3-(2-chloro-5-methoxyphenoxy)
-1,1,2-triiodo-1-propene30 3-phenoxy-1-bromo-1,2-diiodo-1-propene31 3-(p-chlorophenoxy)-1-bromo-
1,2-diiodo-1-propene32 3-(p-bromophenoxy)-1-bromo-
1,2-diiodo-1-propene33 3-(m-chlorophenoxy)-1-bromo-
1,2-diiodo-1-propene34 3-(p-methylphenoxy)-1-bromo-
1,2-diiodo-1-propene35 3-(2,4-dichlorophenoxy)-1-bromo-1,2-diiodo-1-propene36 3-(m-methylphenoxy)-1-bromo-
1,2-diiodo-1-propene37 3-(p-methoxyphenoxy)-1-bromo-1,2-diiodo-1-propene38 3-phenoxy-1-chloro-1,2-diiodo-1 -Propene The compound having the general formula () is as follows: 3-phenoxy-1-halo-1-propyne ()
It is produced by iodoaddition reaction. (In the formula, X and R are the same as those described above.) The typical method for producing the triiodoallyl derivative () of the present invention will be explained in more detail with reference to Examples. Example 3-(3-chlorophenoxy)-1,1,2-triiodo-1-propene 3-(3-chlorophenoxy)-1-iodo-1
- Iodine in an ethanol solution (10 ml) of 1 g of propyne
1.2 g was added and stirred at room temperature for 8 hours. After decolorizing the mixture by adding a 1% aqueous sodium hydrosulfite solution, the mixture was extracted with ethyl acetate. The extract was washed with a 1% aqueous sodium bicarbonate solution, then with water, and then dried. After distilling off the solvent, the oily substance obtained was filtered with silica gel.
The product was purified by column chromatography (eluent: n-hexane:benzene = 10:1) to obtain 0.7 g of the desired product. Melting point 66-67℃ Elemental analysis value (%) C ₉ H ₆ OClI ₃ Calculated value C, 19.78; H, 1.11; Cl, 6.49; I, 69.70 Experimental value C, 20.07; H, 1.14; Cl, 6.42; I , 69.10 The following compound was prepared according to the method of the above example. Compound number Melting point (°C) 1 67-68 2 42-43 4 65-66 5 47-48 13 55-56 21 78-79 24 77-78 37 93-94 The compound having the general formula () It has an insect repellent effect against wood pests such as, and is useful as an anticide. Moreover, the compound having the general formula () is also useful as a fungicide and a preservative. In particular, various industrial raw materials such as wood raw materials, plywood, wet pulp, paper, tatami mats, fibers, leather, adhesives, paints, synthetic resins, etc. In addition, mold grows and propagates, causing contamination and deterioration of the substrate. It can be applied to many products that lose their quality value. The molds that occur on industrial raw materials include:
Typical examples include the genus Penicillium, Aspergius, Rhizopus, Chaetomium, Cladosporium, Fusarium, and Aureobasideum, and many other species are known, including Trichoderma and wood discoloration fungi. However, the molds targeted in this invention are not limited to the above-mentioned molds. Further, as for preservative, it can be used to prevent damage caused by wood rotting fungi and wood soft rotting fungi. The compound of the present invention can be mixed with a carrier and other adjuvants as necessary to form a formulation commonly used as a termiticide and an industrial fungicide/preservative, such as an oil-soluble agent, emulsion, paste, or powder. , hydrating agent,
It is prepared and used in aerosols, paints, etc.
Suitable carriers include inert solid carriers such as clay, talc, pentonite, kaolin, silicic anhydride, calcium carbonate, and wood flour; liquid carriers such as kerosene, ligroin, xylene, methylnaphthalene, dimethylformamide, and dimethyl sulfoxide; and nitrogen. Examples include gas carriers such as gas, dimethyl ether, chlorofluorocarbon gas, and vinyl chloride monomer. Examples of adjuvants that can be used as appropriate to improve the properties of the preparation and enhance its anti-termite, antiseptic, and antifungal effects include anionic, cationic, and nonionic surfactants, methyl cellulose, and vinyl acetate resin. , various polymer compounds such as sodium alginate, etc. Of course, 2-(4-thiazolyl)penzimidazole; N,N-dimethyl-N'-dichlorofluoromethylthio-N'-phenylsulfamide; 4
-chlorophenyl-3'-iodopropargyl formal; halogenated phenolic compounds such as trichlorophenol or tribromophenol; trialkyltin or triaryltin compounds such as bistributyltin oxide, tributyltin phthalate, or triphenyltin hydroxide; N- Metal salts of nitroso-N-cyclohexylamine, such as aluminum salts; xyligen-
B; Or preservatives such as benzanilide compounds.
It can be used in combination with fungicides and insecticides such as organophosphorus compounds such as phoxim; pyrethroid compounds such as permethrin; carbamate compounds such as bigon, and organochlorine compounds such as chlordane. In actual use, the content of the compound of the present invention may vary over a wide range depending on the form of the preparation or the purpose of use, but generally a range of 0.01 to 95%, preferably 0.5 to 70% by weight is appropriate. In addition, termiticides, fungicides, and preservatives can be used on raw materials such as wood and wood materials by dipping, coating, spraying, or injecting, and they can also be mixed into adhesives, etc. , plywood, hardboard,
It can also be processed into particle board, etc. Next, the effectiveness of the termiticide, anti-mold and antiseptic agent of the present invention will be explained using test examples. Test Example 1 Anti-termite Efficacy Test In an indoor anti-termite efficacy test against house termites, a test specimen (Hemlock sapwood, diameter 6.5 mm, thickness 0.2 mm) was added to a 3 W/V% acetone solution of the compound of this invention for 50 minutes.
After soaking for seconds and removing excess solvent with paper,
Air dried for 24 hours. This test specimen was placed in a small sample bottle (inner diameter 1.6 cm, height 2.6 cm), 10 worker ants were placed in it, and the specimen was placed in a dark place at 27°C and a relative temperature of 95% or higher.
The feeding damage was observed for a week. The results are shown in Table 1. The labeling to indicate the degree of anti-termite efficacy is as follows. +: The test specimen does not suffer from feeding damage at all. ±: The test specimen suffered from feeding damage to the extent of traces. −: The test specimen clearly suffered from feeding damage. In addition, in the untreated test, more than 4/5 of the test specimens disappeared due to feeding damage.

[Table] Test Example 2 Antifungal Efficacy Test A 1.0 W/V% dimethylformamide solution of the compound of this invention and pentachlorophenol laurate as a control agent was added to a 1.0 W/V % dimethylformamide solution of Moso bamboo and beech sapwood (both 2 x 2 x 0.2 cm). ) for 5 seconds,
Air dry, wash with water (water supply rate approx. 2/min) for 1 hour, air dry for 24 hours
After heating at 60° C. for 24 hours, the sample was further subjected to dry heat sterilization to prepare a test specimen. A mold resistance test was carried out on this specimen in accordance with the method described in JIS Z 2911 "Mold Resistance Test Method". That is, Aspergillus niger (test bacterium) was used as the test bacterium.
No. 1), Trichoderma viride (No. 1), Trichoderma viride
A total of four types of molds were used: Fusarium moniliforme (Same 2), Fusarium moniliforme (Same 3), and Pullularia pullulans (Same 4). The cells were cultured for 3 weeks at 25°C in a sterile glassware containing water-containing paper, and the efficacy was determined based on the degree of mycelial growth. The results are shown in Table 2. In addition, the labeling to express the antifungal efficacy was as follows. +: No mold growth observed on the sample. ±: Very slight mold growth is observed on the sample. -: Mold growth is observed on the sample.

[Table] Test Example 3 Wood Preservative Efficacy Test In accordance with the method for testing the preservative effect of wood preservatives specified in the Japanese Industrial Standards (JIS A 9302), the compound of this invention and pentachlorophenol as a control agent were tested at 0.05W/each. V% methanol solution was injected under reduced pressure into the test specimen (cedar sapwood, 2 x 2 x 1 cm), air dried, washed with water (water supply rate approximately 2/min) for 5 hours, air dried for 24 hours, and heated at 60℃ for 24 hours. After repeating the weathering operation twice as one cycle, dry heat sterilization was further performed to prepare a test specimen. This test specimen was placed on an agar medium (2% malt extract, 1% glucose, 0.5% heptone) in a sterile shear dish.
The lignin-degrading bacterium Coriolus is grown in advance to test the wood preservative efficacy.
versicolor) and the cellulose-degrading bacterium Tyromyces palustris and forced rot at 25°C for 3 weeks. Efficacy was determined by the degree of mycelial growth on the specimen and the presence or absence of a decrease in compressive strength. . The results are shown in Table 3. The labeling to express the preservative efficacy was as follows. +: No mycelial growth was observed on the test specimen, and the compressive strength was no different from that of healthy material. ±: Slight growth of hyphae was observed on the test specimen, or the compressive strength was slightly reduced. −: Growth of hyphae was observed on the test specimen, or the compressive strength was clearly decreased.

[Table] Next, some formulation examples of the termiticide and antifungal/preservative of the present invention will be given, but it goes without saying that the blending amount, type of auxiliary agent, etc. can be varied considerably. (In the text, all parts simply refer to parts by weight.) Formulation Example 1 Emulsion 10 parts of Compound No. 1 were dissolved in 40 parts of dimethylformamide, and 50 parts of xylene and 10 parts of polyoxyethylene nonyl phenyl ether were added. The mixture was added and thoroughly mixed to obtain an emulsion. This emulsion can be diluted with an appropriate amount of water and used by coating, dipping, or spraying on wood materials to be treated, and can also be applied to the treatment of plywood, particle board, hardboard, etc. with adhesives. Formulation Example 2 Oil Soluble Agent 2 parts of Compound No. 4 was dissolved in 2 parts of dimethylformamide, and 96 parts of solvent naphtha was added to obtain an oil agent. Formulation Example 3 Powder 2 parts of Compound No. 3 were dissolved in 10 parts of acetone, 68 parts of clay and 30 parts of talc were added and mixed uniformly, and the acetone was removed by evaporation to obtain a powder. Formulation Example 4 Wettable powder 40 parts of Compound No. 13, 56 parts of clay, 3 parts of sodium lauryl alcohol sulfonate, and 1 part of polyvinyl alcohol were mixed uniformly in a mixer, and ground in a hammer mill to form a wettable powder. Obtained. Formulation Example 5 Paint 10 parts of compound No. 21, 20 parts of Palite powder,
A paint was obtained by uniformly mixing 10 parts of vinyl resin, 25 parts of pine resin, and 35 parts of xylene. Formulation Example 6 Aerosol 2 parts of Compound No. 1 and 0.5 parts of fragrance are dissolved in 40 parts of deodorized kerosene, filled into an aerosol container, fitted with a valve, and then filled with 58 parts of liquefied petroleum gas under pressure to obtain an aerosol. Ta.

Claims (1)

[Claims] 1 formula (In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a phenyl group with or without 1 to 3 substituents selected from a halogen atom, a lower alkyl group, and a lower alkoxy group) A trihaloallyl derivative having 2 formulas (In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a phenyl group with or without 1 to 3 substituents selected from a halogen atom, a lower alkyl group, and a lower alkoxy group) An anticide containing a trihaloallyl derivative having the following as an active ingredient. 3 formulas (In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a phenyl group with or without 1 to 3 substituents selected from a halogen atom, a lower alkyl group, and a lower alkoxy group) An anti-mold and preservative containing a trihaloallyl derivative having the following as an active ingredient.