JPS6364415B2 - - Google Patents

Description

[Detailed description of the invention]

This invention is a novel 3-chloro-2,3-diio-
The present invention relates to dooryl derivatives and termiticides, pest repellents, and antifungal/preservatives containing the derivatives as active ingredients. Japanese Patent Publication No. 53-20484 points out that 2,3,3-triiodoallyl alcohol is useful as an industrial disinfectant and antifungal agent. In addition, in Special Publication No. 53-20006, the general formula (In the formula, R ₁ represents a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.) Alkyl-2,3,3-triiodoallyl ether represented by the following is disclosed and has antibacterial properties. It has been known. However, nothing has been said about the control efficacy of these compounds against termites, which are important wood pests, or the repellent efficacy against sanitary pests such as cockroaches, flies, and mosquitoes. This new 3-chloro-2,3-diiodoallyl derivative has the formula () (wherein R represents formyl, lower alkanoyl, or lower alkoxycarbonyl group). R is preferably a formyl group, a linear or branched lower alkanoyl group having 2 to 5 carbon atoms such as acetyl, propionyl, isopropionyl, butyryl, isobutyryl, and valeryl; methoxycarbonyl, ethoxycarbonyl, n -propoxycarbonyl, i-propoxycarbonyl, n-
It represents a straight or branched alkoxycarbonyl group having 2 to 5 carbon atoms such as butoxycarbonyl. More preferably, R is a formyl, acetyl, propionyl, methoxycarbonyl, or ethoxycarbonyl group. 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-formyloxy-1-chloro-1,2-
diiodo-1-propene 2 3-acetoxy-1-chloro-1,2-diiodo-1-propene 3 3-propionyloxy-1-chloro-1,
2-diiodo-1-propene4 3-isopropionyloxy-1-chloro-
1,2-diiodo-1-propene 5 3-butyryloxy-1-chloro-1,2-
Diiodo-1-propene 6 3-isobutyryloxy-1-chloro-1,
2-diiodo-1-propene 7 3-valeryloxy-1-chloro-1,2-
Diiodo-1-propene 8 3-methoxycarbonyloxy-1-chloro-1,2-diiodo-1-propene 9 3-ethoxycarbonyloxy-1-chloro-1,2-diiodo-1-propene 10 3-n- Propoxycarbonyloxy-1-
Chloro-1,2-diiodo-1-propene 11 3-i-propoxycarbonyloxy-1-
Chloro-1,2-diiodo-1-propene 12 3-n-butoxycarbonyloxy-1-chloro-1,2-diiodo-1-propene In the new compound () according to this invention, R is an alkanoyl group, alkoxycarbonyl In the case of a group, as shown in the following reaction formula, 3-chloro2,3-diiodoallyl alcohol () obtained by the iodine addition reaction of 3-chloropropargyl alcohol () is combined with an acid halide or chlorocarbonate. When R is a formyl group, it is obtained by reacting with formic acid. (In the formula, X represents a halogen, and R ₁ represents a lower alkyl group or a lower alkoxy group.)
The method for producing the dooryl derivative (2) will be explained in more detail with reference to Examples. Note that the Rf value indicates the value obtained by thin layer chromatography using a developing solvent of ethyl acetate:n-hexane=1:5. Example 1 3-Formyloxy-1-chloro-1,2-diiodo-1-propene 8.4 g of iodine was added to 30 ml of an aqueous solution of 3.02 g of 3-chloropropargyl alcohol, and the mixture was stirred at room temperature for 6 hours. The precipitated crystals were collected, washed with water, and then dried. Melting point: 113℃ after recrystallization from ethyl acetate-n-hexane
9.8 g of 3-chloro-2,3-diiodoallyl alcohol having the following properties was obtained. After refluxing 1.7 g of this alcohol with 25 ml of formic acid for 5 hours, it was poured into ice water, neutralized with sodium bicarbonate, and extracted with ethyl acetate. After the extract was dried, the solvent was distilled off, and the obtained crystals were recrystallized from n-hexane to obtain 1.5 g of the target compound having a melting point of 45°C. Infrared absorption spectrum (Nujol) 1700, 1720 cm ^-1 Elemental analysis value (%) As C ₄ H ₃ O ₂ ClI ₂ Calculated value; C, 12.90, H; 0.81; Cl, 9.52; I, 68.17 Experimental value; 12.99; H, 0.91; Cl, 9.48; I, 67.95 Example 2 3-acetoxy-1-chloro-1,2-diiodo-1-propene 3-chloro 2,3-diiodoallyl alcohol
Dissolve 3.4g in 10ml of pyridine and add acetic anhydride under cooling.
After adding 1.5 g, it was left to stand at room temperature overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate.
The extract was washed with an aqueous copper sulfate solution and water, dried, and the solvent was distilled off to obtain 3.9 g of the target compound as an oil. Infrared absorption spectrum (Liq): 1740 cm ^-1 Elemental analysis value (%) As C ₅ H ₅ O ₂ ClI ₂ Calculated value: C, 15.54; H, 1.30; Cl, 9.18; I, 65.69 Experimental value: C, 15.84 ; H, 1.45; Cl, 8.90; I, 65.81 Rf value: 0.56 The following compound was produced according to the method of the above example. The compound numbers are the same as those given to the exemplified compounds above.

[Table] The compound having the general formula () has an insect repellent effect against wood pests such as termites and is useful as a termiticide. Furthermore, the compound having the general formula () has an excellent repellent effect against pests, and is particularly useful as a repellent for pests such as cockroaches, flies, and mosquitoes. Furthermore, the compound having the general formula () is also useful as a fungicide and 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 termiticides, pest repellents, and industrial fungicides/preservatives, such as oil-soluble agents, emulsions, etc. It is prepared and used in pastes, powders, solids, wettable powders, smokers, aerosols, paints, etc. Suitable carriers include inert solid carriers such as clay, talc, bentonite, kaolin, silicic anhydride, calcium carbonate, and wood flour; liquid carriers such as kerosene, ligroin, xylene, methylnaphthalene, dimethylformamide, and dimethyl sulfoxide; and nitrogen gas. , dimethyl ether, chlorofluorocarbon gas, vinyl chloride monomer, and the like. Examples of auxiliary agents that can be used as appropriate to improve the properties of the preparation and enhance its anti-termite, repellent, antiseptic, and antifungal effects include anionic, cationic, and nonionic surfactants, methyl cellulose, and acetic acid. Examples include various polymeric compounds such as vinyl resin and sodium alginate. Of course, 2-(4-thiazolyl)benzimidazole; 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.
Antifungal agents, phoxim, toction, zertel,
Organophosphorus compounds such as diazinon and sumithion;
Pyrethroid compounds such as permethrin and huenvalerate; carbamate compounds such as bigon and sevin; organochlorine compounds such as dichlorobenzene and chlordane; insecticides such as naphthalene and camphor; stabilizers, synergists, and diethyl tol. Amido, Tabtrex, Letspar 111, Letspar
It can be used in combination with other repellents such as 333, R-874, and R-1207, fragrances, nonvolatile carriers, and the like. 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 treated by dipping, coating, spraying, or injecting raw materials such as wood and wood materials, or by mixing them into adhesives, etc. , plywood, hardboard,
It can also be processed into particle boats, etc. Furthermore, in addition to treating raw materials such as wood and wood materials in the same manner as above, the repellent can also be sprayed, applied, or Methods such as smoking, placing paper strips, cloth strips, microcapsules, or rod-shaped molded bodies containing the compound of the present invention, or pasting tape can be used. It can also be applied to entire areas where you want to avoid infestation. Furthermore, it can be applied to the skin of humans and animals as a lotion, cream or QB aerosol against mosquitoes, and can also be applied to clothing, towels and packaging materials. Next, the efficacy of the termiticide, repellent, and antifungal/preservative 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 added, and the sample was placed in a dark place at 27°C and a relative humidity 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 Repellent efficacy test against cockroaches Compound 2W/ of the present invention was applied to the inner bottom surface (9 x 5 cm ² ) of a shelter (9 x 5 x 1 cm ² ) made of Mino Hoshi.
After uniformly applying 0.5 ml of V% acetone solution and letting it air dry, place it in the center of a 20 x 22 x 30 cm ² glass container, and place 5 large black cockroach larvae in the container.
The repellent effect was investigated based on cockroach behavior over a 24-hour period. The results are shown in Table 2. The display indicating the repelling effect was as follows. +: Cockroaches do not sneak into the shelter at all. ±: Traces of cockroaches temporarily infiltrating the shelter are observed. −: One or more cockroaches always sneaked into the shelter.

[Table] Test Example 3 Antifungal efficacy test Pentachlorophenol-laurate each 1.0W/V% as a compound of this invention and a control drug
Soak bamboo bamboo and beech sapwood (both 2 x 2 x 0.2 cm) in dimethylformamide solution 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 conducted on this test specimen in accordance with the method described in JIS Z2911 "Mold Resistance Test Method". That is, Aspergillus niger (test bacteria No.
1), Trichoderma viride
Using a total of four types of molds: Fusarium moniliforme (Same 2), Fusarium moniliforme (Same 3), and Pullularia pullulans (Same 4), a mold suspension was inoculated onto the test specimen. The cells were then cultured at 25°C for 3 weeks 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 3. 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 4 Wood Preservative Efficacy Test Based on the preservative effect testing method for wood preservatives specified in the Japanese Industrial Standards (JIS A9302), the compound of this invention and pentachlorophenol as a control agent were tested at 0.05 W/V each. % methanol solution was injected under reduced pressure into a 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, which is a test bacterium for wood preservative efficacy, was grown in advance on
versicolor) and the cellulose-degrading bacterium Thromyces palustris (Thromyces 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 4. 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, termiticides, repellents, and mold-proofing agents of this invention
Some examples of formulations of preservatives will be given, but it goes without saying that the amount, type of adjuvant, etc. can vary widely. (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. Furthermore, it can be applied to entire areas where pests do not want to live. Formulation Example 2 Oil Soluble Agent 2 parts of Compound No. 2 was dissolved in 2 parts of dimethylformamide, and 96 parts of solvent naphtha was added to obtain an oil agent. This oil is used by spraying, coating, dipping, injecting, etc. on raw materials such as wood materials to be treated and habitats of cockroaches, mosquitoes, etc. Formulation Example 3 Powder 2 parts of Compound No. 9 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. 8, 56 parts of clay, 3 parts of sodium lauryl alcohol sulfonate, and 1 part of polyvinyl alcohol were mixed uniformly in a mixer, ground with a hammer mill, and mixed with water. I got Japanese medicine. Formulation Example 5 Paint 10 parts of compound No. 3, 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. 2 and 0.5 part of fragrance were 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. .

Claims (1)

[Claims] 1 formula (wherein, R represents formyl, lower alkanoyl, or lower alkoxycarbonyl group)
Chloro-2,3-diiodoallyl derivative. 2 formulas (wherein, R represents formyl, lower alkanoyl, or lower alkoxycarbonyl group)
An anticide containing a chloro-2,3-diiodoallyl derivative as an active ingredient. 3 formulas (wherein, R represents formyl, lower alkanoyl, or lower alkoxycarbonyl group)
A pest repellent containing a chloro-2,3-diiodoallyl derivative as an active ingredient. 4 formula (wherein, R represents formyl, lower alkanoyl, or lower alkoxycarbonyl group)
An anti-mold and preservative containing a chloro-2,3-diiodoallyl derivative as an active ingredient.