JP4558496B2 - Bactericidal composition for controlling rice plant diseases - Google Patents
Bactericidal composition for controlling rice plant diseases Download PDFInfo
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- JP4558496B2 JP4558496B2 JP2004548069A JP2004548069A JP4558496B2 JP 4558496 B2 JP4558496 B2 JP 4558496B2 JP 2004548069 A JP2004548069 A JP 2004548069A JP 2004548069 A JP2004548069 A JP 2004548069A JP 4558496 B2 JP4558496 B2 JP 4558496B2
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- rice
- bactericidal composition
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
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- FNENWZWNOPCZGK-UHFFFAOYSA-N ethyl 2-methyl-3-oxobutanoate Chemical compound CCOC(=O)C(C)C(C)=O FNENWZWNOPCZGK-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UFEODZBUAFNAEU-NLRVBDNBSA-N fluoxastrobin Chemical compound C=1C=CC=C(OC=2C(=C(OC=3C(=CC=CC=3)Cl)N=CN=2)F)C=1C(=N/OC)\C1=NOCCO1 UFEODZBUAFNAEU-NLRVBDNBSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000008099 melanin synthesis Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JHIPUJPTQJYEQK-ZLHHXESBSA-N orysastrobin Chemical compound CNC(=O)C(=N\OC)\C1=CC=CC=C1CO\N=C(/C)\C(=N\OC)\C(\C)=N\OC JHIPUJPTQJYEQK-ZLHHXESBSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- RCMHUQGSSVZPDG-UHFFFAOYSA-N phenoxybenzene;phosphoric acid Chemical class OP(O)(O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 RCMHUQGSSVZPDG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- IBSNKSODLGJUMQ-SDNWHVSQSA-N picoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1COC1=CC=CC(C(F)(F)F)=N1 IBSNKSODLGJUMQ-SDNWHVSQSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 235000019814 powdered cellulose Nutrition 0.000 description 1
- 229920003124 powdered cellulose Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- QQKDTTWZXHEGAQ-UHFFFAOYSA-N propyl carbonochloridate Chemical compound CCCOC(Cl)=O QQKDTTWZXHEGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012363 selectfluor Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LWLJEQHTPVPKSJ-UHFFFAOYSA-N tebufloquin Chemical compound C1=C(C(C)(C)C)C=C2C(OC(=O)C)=C(C)C(C)=NC2=C1F LWLJEQHTPVPKSJ-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Quinoline Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
発明の分野
本発明は、優れた水稲病害に対して優れた防除効果を示す殺菌性組成物に関する。より詳しくは、本発明は、イネいもち病をはじめとする糸状菌性の水稲病害に対して優れた防除効果を示す殺菌性組成物に関する。
FIELD OF THE INVENTION The present invention relates to a bactericidal composition exhibiting an excellent control effect against excellent paddy rice diseases. More specifically, the present invention relates to a bactericidal composition exhibiting an excellent control effect against fungal paddy rice diseases such as rice blast.
関連技術
本出願人による国際公開ＷＯ０１／９２２３１号公報（国際公開日：2001/12/06）には、優れた殺菌活性を有する下記式（１）で表される化合物またはその酸付加塩が開示されている：
式（１）で表される化合物の作用メカニズムは、未だその詳細は明らかになっていない。しかしながら、カスガマイシン、有機リン剤、およびストロビルリン系化合物に対して耐性を有する耐性菌に対しても防除効果を示すこと、および、培地内においてメラニンの生合成を阻害せずに殺菌活性を示すことなどから、既存のイネいもち病防除剤とは異なる作用メカニズムを有すると推測される。 The details of the action mechanism of the compound represented by the formula (1) have not yet been clarified. However, it also has a controlling effect against resistant bacteria having resistance to kasugamycin, organophosphates, and strobilurin compounds, and exhibits bactericidal activity without inhibiting melanin biosynthesis in the medium. Therefore, it is estimated that it has a different mechanism of action from existing rice blast control agents.
イネいもち病をはじめ複数の糸状菌性水稲病害、または、ムギ類、野菜、果樹の栽培上問題となる種々の糸状菌性病害もしくはその病原菌に対して、優れた防除効果または高い殺菌活性を示す化合物として、ストロビルリン系の殺菌剤化合物が報告されている。ストロビルリン系化合物がこのように優れた防除効果を有すること、およびその作用メカニズムに関しては、例えば、農薬ハンドブック２００１年版（２００１年、社団法人日本植物防疫協会発行）、および、一般委託試験成績書（社団法人日本植物防疫協会発行）などに記載されている。 Excellent control effect or high bactericidal activity against rice blast disease and other fungal fungal diseases, or various fungal diseases that cause problems in the cultivation of wheat, vegetables and fruit trees or their pathogens As a compound, a strobilurin-based fungicide compound has been reported. With regard to the fact that the strobilurin-based compound has such an excellent control effect and its action mechanism, for example, the Agricultural Chemicals Handbook 2001 version (2001, issued by the Japan Plant Protection Association) and the general contract test report (corporate association) Issued by the Japan Plant Protection Association).
イネいもち病は、水稲栽培において最も被害の大きい病害である。いもち病は、糸状菌の一種で、不完全菌類に属するPyricularia属菌の寄生により起こる植物の病気である。これまでに多くの優れたイネいもち病に対する防除薬剤や防除方法が報告されている。 Rice blast is the most damaging disease in rice cultivation. Rice blast is a type of filamentous fungus that is a plant disease caused by the infestation of Pyricularia spp. So far, many excellent control agents and control methods for rice blast have been reported.
しかしながら、冷害、長梅雨などの気象条件や、育苗、施肥における管理の不徹底などの栽培条件によっては、このような防除剤を使用した場合であっても、イネいもち病が大発生してしまう場合も見受けられた。このため、防除効果がさらに優れた防除剤の開発が望まれている。また近時、農家の兼業化や農業従事者の高齢化がいっそう進んでいるため、病害防除実施期間の延長や散布回数、労力を軽減する技術が必要となっている。また、作業の省力化および散布農薬量を低減させる目的で、複数の病害に対して同時に防除効果を示し得る薬剤の開発が望まれている。 However, depending on the weather conditions such as cold damage and long rainy season, and cultivation conditions such as inadequate management in raising seedlings and fertilization, rice blast may occur even when such control agents are used. A case was also seen. For this reason, development of the control agent which was further excellent in the control effect is desired. In addition, as farmers become part-time workers and farmers are aging more and more recently, technology is required to extend the disease control period, reduce the number of sprays, and reduce labor. In addition, for the purpose of saving labor and reducing the amount of agricultural chemicals sprayed, it is desired to develop a drug capable of simultaneously controlling a plurality of diseases.
本発明者らは今般、前述した複数の活性およびそれら活性の持続期間などを総合した効果を評価することにより、前記式（１）の化合物（２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−キノリノール誘導体）と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物と含んでなる混合組成物が、各成分が活性を損なわないばかりか、相乗的な効果を発揮して、優れたイネいもち病の防除効果を示すことを見出した。このとき、該組成物は、代表的な水稲病害であるイネいもち病に対し散布適期に適用された場合のみならず、散布時期が遅れた場合においても、低薬量で、長期間に渡って優れた防除効果を示すことがわかった。本発明はかかる知見に基づくものである。 The inventors of the present invention have now evaluated the compound (2,3-dimethyl-6-t-butyl-8) of the above formula (1) by evaluating the combined effects of the plurality of activities described above and the duration of the activities. -Fluoro-4-quinolinol derivative) and at least one compound selected from strobilurin fungicides, not only does each component impair the activity, but also exhibits a synergistic effect. The present inventors have found that it has an excellent control effect on rice blast. At this time, the composition is not only applied to the rice blast disease, which is a typical rice plant disease, in an appropriate spraying period, but also at a low dosage and over a long period even when the spraying time is delayed. It was found that it exhibits an excellent control effect. The present invention is based on such knowledge.
よって本発明は、優れた水稲病害防除効果を有する薬剤であって、散布時期が遅れた場合においても低薬量で長期間にわたって優れた防除効果を示すことができる薬剤の提供をその目的とする。 Accordingly, an object of the present invention is to provide a drug having an excellent paddy rice disease control effect, which can exhibit an excellent control effect over a long period of time with a low dosage even when the spraying time is delayed. .
本発明による殺菌性組成物は、下記式（１）：
の化合物またはその酸付加塩と、
ストロビルリン系殺菌剤から選択される少なくとも１種の化合物と
を有効成分として含んでなるものである。
The bactericidal composition according to the present invention has the following formula (1):
Or an acid addition salt thereof,
It comprises at least one compound selected from strobilurin fungicides as an active ingredient.
本発明によるイネ病害の防除方法は、前記殺菌性組成物の有効量を、処理すべき領域に適用することを含んでなるものである。 The method for controlling rice diseases according to the present invention comprises applying an effective amount of the bactericidal composition to the area to be treated.
本発明によれば、水稲病害の防除剤を製造するため、前記殺菌性組成物の使用が提供される。 According to the present invention, use of the bactericidal composition is provided for producing a paddy rice disease control agent.
本発明による殺菌性組成物は、作用機序や殺菌スペクトルの異なる２種の化合物を混合してなる。本発明による殺菌性組成物は、イネいもち病のみならず、紋枯病、ごま葉枯病菌やすじ葉枯病菌などによる穂枯れ、Curvularia属菌やAlternaria属菌などによる変色米、稲こうじ病などの、他の糸状菌性水稲病害に対しても、優れた防除効果を有する。本発明によれば、殺菌性組成物の各成分が相乗的に作用して予想外の顕著な防除効果を発揮することができる。よって、本発明の殺菌性組成物によれば、面積当りの施用薬量を減少させることができる。本発明の殺菌性組成物によれば、その成分をそれぞれ単独使用する場合に比べて、より少ない薬量の使用で優れた防除効果を発揮できる。またその効果は長期間にわたって有効である。このため、本発明の殺菌性組成物によれば、植物を処理する回数を減らすことができ、また、栽培期間中に対象となる植物に対して使用する薬剤の総量を減少させることができる。本発明の殺菌性組成物は、散布適期に防除処理がなされた場合のみならず、散布時期が遅れた場合においても優れた防除効果を示すことができる。本発明による殺菌性組成物は、複数の病害の同時防除が可能であり、また菌の耐性化が起こるリスクを低減することができる。本発明による殺菌性組成物は、農業の省力化、環境の保護および食料生産の安定において大きな貢献が期待できる。 The bactericidal composition according to the present invention is a mixture of two compounds having different action mechanisms and bactericidal spectra. The bactericidal composition according to the present invention is not limited to rice blast, but also stem blight, sesame leaf blight fungus and leaf blight fungus etc., withered rice, Curvularia spp., Alternaria spp. It has an excellent control effect against other filamentous fungal paddy rice diseases. According to this invention, each component of a bactericidal composition can act synergistically and can exhibit the unexpected remarkable control effect. Therefore, according to the bactericidal composition of the present invention, the amount of applied medicine per area can be reduced. According to the bactericidal composition of the present invention, it is possible to exert an excellent control effect by using a smaller dosage compared to the case where each of the components is used alone. The effect is effective over a long period of time. For this reason, according to the bactericidal composition of this invention, the frequency | count of processing a plant can be reduced, and the total amount of the chemical | medical agent used with respect to the plant used as object during a cultivation period can be reduced. The bactericidal composition of the present invention can exhibit an excellent control effect not only when the control treatment is performed at the appropriate spraying time but also when the spraying time is delayed. The bactericidal composition according to the present invention can simultaneously control a plurality of diseases and can reduce the risk of resistance to bacteria. The bactericidal composition according to the present invention can be expected to greatly contribute to the labor saving of agriculture, environmental protection and food production stability.
殺菌性組成物
本発明による殺菌性組成物は、前記したように、式（１）の化合物またはその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物とを有効成分として含んでなるものである。
Bactericidal composition As described above, the bactericidal composition according to the present invention contains, as active ingredients, the compound of formula (1) or an acid addition salt thereof and at least one compound selected from strobilurin fungicides. It is what.
この殺菌性組成物は、植物の病害、好ましくはイネ病害、より好ましくは水稲病害、の防除に用いることができる。このような病害としては、例えば、イネいもち病、ごま葉枯病菌やすじ葉枯病菌などによる穂枯れ、Curvularia属菌やAlternaria属菌などによる変色米、稲こうじ病、および紋枯病などが挙げられる。より好ましくは、本発明による殺菌性組成物は、イネいもち病の防除に用いられる。 This bactericidal composition can be used for controlling plant diseases, preferably rice diseases, more preferably paddy rice diseases. Such diseases include, for example, rice blast, sesame leaf blight fungus and leaf blight fungus, etc., withered rice, Curvularia spp., Alternaria spp. It is done. More preferably, the bactericidal composition according to the present invention is used for controlling rice blast.
ここで「有効成分として含んでなる」とは、所望する剤型に応じた担体を含んでいてもよいことは当然として、併用可能な他の薬剤を含有する場合も包含することを意味する。 Here, “comprising as an active ingredient” means that a carrier corresponding to a desired dosage form may be included, and naturally includes a case where it contains other drugs that can be used in combination.
ここで「イネ」は、水稲および陸稲を包含する意味で用いられる。また「水稲」とは、水田で栽培される稲のことをいう。 Here, “rice” is used to include paddy rice and upland rice. In addition, “paddy rice” refers to rice cultivated in paddy fields.
式（１）の化合物
本発明による殺菌性組成物は、前記式（１）の化合物またはその酸付加塩を含んでなるものである。
Compound of Formula (1) The bactericidal composition according to the present invention comprises the compound of formula (1) or an acid addition salt thereof.
式（１）において、Ｒは、水素原子、−ＣＯＲ１、−ＣＯＯＲ１、−ＣＯＣＨ２ＯＣＨ３、または−ＣＯＣＨ２ＯＣＯＣＨ３を示す。ここでＲ１は炭素数１〜４のアルキル基である。本発明において、アルキル基は、直鎖状、分岐鎖状、または環状のいずれの形式であってもよく、また必要により、アルキル上の１またはそれ以上の水素原子が１またはそれ以上の置換基（同一または異なっていてもよい）により置換されていてもよい。Ｒ１の具体例としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、またはｎ−ブチル基が挙げられる。 In the formula (1), R represents a hydrogen atom, —COR 1 , —COOR 1 , —COCH 2 OCH 3 , or —COCH 2 OCOCH 3 . Here, R 1 is an alkyl group having 1 to 4 carbon atoms. In the present invention, the alkyl group may be linear, branched, or cyclic, and if necessary, one or more hydrogen atoms on the alkyl are one or more substituents. (May be the same or different). Specific examples of R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group.
式（１）中においてＲが水素原子である場合には、式（１）の化合物は、その互変異性体である下記式（２）に示される構造をとることができる。式（１）の化合物が、前記式（２）の化合物を包含することは当業者にも明らかである。
本発明において、「酸付加塩」とは、例えば塩酸塩、硝酸塩、硫酸塩、リン酸塩、酢酸塩等の一般的に農園芸分野において使用可能な塩を意味する。 In the present invention, the “acid addition salt” means a salt that can generally be used in the field of agriculture and horticulture such as hydrochloride, nitrate, sulfate, phosphate, acetate, and the like.
なお、式（１）の化合物は、水和物または溶媒和物の形態をとることも可能であり、本発明においては、そのような水和物および溶媒和物も式（１）の化合物に包含される。 In addition, the compound of Formula (1) can also take the form of a hydrate or a solvate. In the present invention, such a hydrate and a solvate are also included in the compound of Formula (1). Is included.
式（１）の化合物の具体例としては、後述する実施例の化合物１〜１１が挙げられる。 Specific examples of the compound of formula (1) include compounds 1 to 11 of Examples described later.
式（１）の化合物の製造方法
式（１）の化合物は、結合の形成ないし置換基の導入に関して、合目的的な任意の方法によって合成することができる。
Method for Producing Compound of Formula (1) The compound of formula (1) can be synthesized by any method suitable for forming a bond or introducing a substituent.
式（１）の化合物は、例えば、既知の方法で合成可能な４−ｔ−ブチル−２−フルオロアニリンから、以下のスキームに従って製造することができる。
Ｒは、水素原子、−ＣＯＲ１、−ＣＯＯＲ１、−ＣＯＣＨ２ＯＣＨ３、または−ＣＯＣＨ２ＯＣＯＣＨ３であり、
Ｒ１は、炭素数１〜４のアルキル基であり、
Ｒ２は、−Ｒ１、−ＯＲ１、−ＣＨ２ＯＣＨ３、または−ＣＨ２ＯＣＯＣＨ３である］。
The compound of the formula (1) can be produced, for example, from 4-t-butyl-2-fluoroaniline that can be synthesized by a known method according to the following scheme.
R is a hydrogen atom, —COR 1 , —COOR 1 , —COCH 2 OCH 3 , or —COCH 2 OCOCH 3 ;
R 1 is an alkyl group having 1 to 4 carbon atoms,
R 2 is —R 1 , —OR 1 , —CH 2 OCH 3 , or —CH 2 OCOCH 3 ].
このスキームは、先ず、式（２）の化合物を用意し（工程(a)）、次いで必要により、この式（２）の化合物を、式（３）または式（４）の化合物と、塩基存在下若しくは塩基非存在下において反応させる（工程(b)）ことによって、式（１）の化合物を得るものである。 In this scheme, first, a compound of the formula (2) is prepared (step (a)), and if necessary, the compound of the formula (2) is combined with a compound of the formula (3) or the formula (4) and a base is present. The compound of the formula (1) is obtained by reacting in the absence of a base or in the absence of a base (step (b)).
上記スキームを具体的に説明すると、下記の通りである。 The above scheme will be specifically described as follows.
工程(a)：
先ず、４−ｔ−ブチル−２−フルオロアニリンと２−メチルアセト酢酸エチルとから、例えば、J. Am. Chem. Soc. 70, 2402 (1948)、Tetrahedron Lett. 27, 5323 (1986)に準じて、式（２）の化合物を得る。なお、この式（２）の化合物は、式（１）の化合物においてＲが水素原子である化合物に相当する。また使用される４−ｔ−ブチル−２−フルオロアニリンは、例えば、Chem. Abs. 42, 2239またはJ. Chem. Soc.,Chem. Commun., 1992, 595に記載の公知の方法により得ることができる。
Step (a):
First, from 4-t-butyl-2-fluoroaniline and ethyl 2-methylacetoacetate, for example, according to J. Am. Chem. Soc. 70, 2402 (1948), Tetrahedron Lett. 27, 5323 (1986). To obtain a compound of formula (2). The compound of the formula (2) corresponds to the compound in which R is a hydrogen atom in the compound of the formula (1). The 4-t-butyl-2-fluoroaniline used is obtained by a known method described in, for example, Chem. Abs. 42, 2239 or J. Chem. Soc., Chem. Commun., 1992, 595. Can do.
工程(b)：
次いで、式（１）においてＲが水素原子以外の化合物を所望する場合には、式（３）または式（４）の化合物で塩基存在下若しくは塩基非存在下で反応させることにより、式（１）の化合物を製造することができる。
Step (b):
Next, when a compound in which R is other than a hydrogen atom in the formula (1) is desired, the compound of the formula (1) is reacted with the compound of the formula (3) or (4) in the presence or absence of a base. ) Can be produced.
ここで、使用可能な塩基としては、例えば、トリエチルアミン、ピリジン等の有機アミン、炭酸ナトリウム、炭酸カリウム、水素化ナトリウム等の無機塩基が挙げられる。また、式（３）または式（４）の化合物は、式（２）の化合物に対して１〜５０当量、好ましくは１〜１０当量の範囲で用いることが望ましい。工程(b)の反応は、無溶媒または反応に関与しない有機溶媒中、例えばジメチルホルムアミドまたはテトラヒドロフラン中において、例えば０〜１４０℃の範囲の温度で実施することができる。 Examples of the base that can be used include organic amines such as triethylamine and pyridine, and inorganic bases such as sodium carbonate, potassium carbonate, and sodium hydride. Further, the compound of formula (3) or formula (4) is used in an amount of 1 to 50 equivalents, preferably 1 to 10 equivalents, relative to the compound of formula (2). The reaction of step (b) can be carried out in the absence of solvent or in an organic solvent that does not participate in the reaction, such as dimethylformamide or tetrahydrofuran, for example, at a temperature in the range of 0 to 140 ° C.
ストロビルリン系殺菌剤
本発明において、ストロビルリン系殺菌剤は、ストロビルリン系の殺菌剤として、当該技術分野において公知のものであれば、いずれのものであってもよい。ストロビルリン系殺菌剤は、例えば、農薬ハンドブック２００１年版（２００１年、社団法人日本植物防疫協会発行）、および、農薬要覧（２００１年、社団法人日本植物防疫協会発行）などに殺菌剤として記載されている。当業者であれば、これら文献を参照することによって、ストロビルリン系殺菌剤を適宜選択することができよう。
Strobilurin fungicide In the present invention, the strobilurin fungicide may be any strobilurin fungicide as long as it is known in the art as a strobilurin fungicide. The strobilurin fungicide is described as a fungicide in, for example, the Agricultural Handbook 2001 (2001, issued by the Japan Plant Protection Association) and the Agricultural Handbook (2001, issued by the Japan Plant Protection Association). . A person skilled in the art will be able to select a strobilurin fungicide as appropriate by referring to these documents.
本発明において使用可能なストロビルリン系殺菌剤の具体例としては、アゾキシストロビン(azoxystrobin)、メトミノストロビン(metominostrobin)、クレソキシムメチル(kresoxim-methyl)、トリフロキシストロビン(trifloxystrobin)、オリサストロビン(orysastrobin)、フルオキサストロビン(fluoxastrobin)、プラクロストロビン(pyraclostrobin)、およびピコキシストロビン(picoxystrobin)が挙げられる。 Specific examples of the strobilurin fungicides that can be used in the present invention include azoxystrobin, metominostrobin, cresoxim-methyl, trifloxystrobin, orysastrobin Fluoxastrobin, pyraclostrobin, and picoxystrobin.
本発明の好ましい態様によれば、ストロビルリン系殺菌剤は、アゾキシストロビン、メトミノストロビン、またはオリサストロビンから選択される。 According to a preferred embodiment of the present invention, the strobilurin fungicide is selected from azoxystrobin, metminostrobin, or orisatrobin.
本発明のより好ましい態様によれば、ストロビルリン系殺菌剤は、アゾキシストロビン、またはメトミノストロビンから選択される。 According to a more preferred embodiment of the present invention, the strobilurin fungicide is selected from azoxystrobin or metminostrobin.
他の成分
本発明による殺菌性組成物を実際に施用する場合には、前記有効成分のみからなる組成物をそのまま用いてもよいが、適当な担体または補助剤をさらに加えて、粉剤、粒剤、パック剤、水和剤、顆粒水和剤、フロアブル剤、液剤、マイクロカプセル剤、乳剤などの任意の剤型に調製して使用することができる。これにより、本発明による殺菌性組成物を、目的に応じた各種の用途に好適に使用することができる。
Other components When the fungicidal composition according to the present invention is actually applied, the composition comprising only the active ingredient may be used as it is, but a suitable carrier or auxiliary agent may be further added to form a powder or granule. , Packs, wettable powders, granular wettable powders, flowables, liquids, microcapsules, emulsions and the like. Thereby, the bactericidal composition by this invention can be used conveniently for the various uses according to the objective.
製剤化は、一般的な農薬における場合と同様にして、当該技術分野において公知の方法にしたがって行うことができる。具体的には例えば、製剤化は、有効成分を、必要に応じて固体担体、溶剤、界面活性剤およびその他の補助剤などと混合することにより行うことができる。これら担体等は、製剤物性の改良、有効成分の安定化、効力増強などの目的に応じて選択することができる。 Formulation can be carried out in accordance with a method known in the art in the same manner as in general agricultural chemicals. Specifically, for example, the formulation can be performed by mixing the active ingredient with a solid carrier, a solvent, a surfactant, and other adjuvants as necessary. These carriers and the like can be selected according to purposes such as improving the physical properties of the preparation, stabilizing the active ingredient, and enhancing the efficacy.
固体担体としては、例えば、クレー、タルク、炭酸カルシウム、珪藻土、ゼオライト、ベントナイト、酸性白土、活性白土、アタパルガスクレー、バーミキュライト、パーライト、軽石、ホワイトカーボン、二酸化チタン、水溶性塩類、木粉、トウモロコシ穂軸、クルミ殻、粉末セルロース、でんぷん、デキストリン、および糖類などが挙げられる。 Examples of the solid carrier include clay, talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acid clay, activated clay, attapulgus clay, vermiculite, perlite, pumice, white carbon, titanium dioxide, water-soluble salts, wood powder, Examples include corn cobs, walnut shells, powdered cellulose, starch, dextrin, and sugars.
溶剤としては、例えば、キシレン、Ｃ９アルキルベンゼン、Ｃ１０アルキルベンゼン、アルキルナフタレン、および高沸点の芳香族炭化水素のような芳香族溶剤；ノルマルパラフィン、イソパラフィン、およびナフテンのような脂肪族溶剤；ケロシンや灯油より製造される溶剤のような混合溶剤；高沸点の脂肪族炭化水素のようなマシン油；エタノール、イソプロパノール、シクロヘキサノールのようなアルコール類、エチレングリコール、ジエチレングリコール、プロピレングリコール、ヘキシレングリコール、ポリエチレングリコール、およびポリプロピレングリコールのような多価アルコール類；プロピレン系グリコールエーテルのような多価アルコール誘導体；シクロヘキサノン、およびγ−ブチロラクトンのようなケトン類；脂肪酸メチルエステル（例えばヤシ油脂肪酸メチルエステル）、および二塩基酸メチルエステル（例えばコハク酸ジメチルエステル、グルタミン酸ジメチルエステル、アジビン酸ジメチルエステル）のようなエステル類；Ｎ−アルキルピロリドンのような窒素含有溶剤；ヤシ油、大豆油、および菜種油のような油脂；および水などが挙げられる。 As the solvent, for example, xylene, C 9 alkylbenzenes, C 10 alkyl benzene, alkyl naphthalene, and aromatic solvents such as high boiling aromatic hydrocarbons; Ya kerosene; normal paraffin, aliphatic solvents such as isoparaffins, and naphthenes Mixed solvents such as solvents produced from kerosene; machine oils such as high-boiling aliphatic hydrocarbons; alcohols such as ethanol, isopropanol and cyclohexanol; ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene Polyhydric alcohols such as glycol and polypropylene glycol; Polyhydric alcohol derivatives such as propylene glycol ethers; Ketones such as cyclohexanone and γ-butyrolactone; Fat Esters such as acid methyl esters (eg palm oil fatty acid methyl esters) and dibasic acid methyl esters (eg succinic acid dimethyl ester, glutamic acid dimethyl ester, adibic acid dimethyl ester); nitrogen-containing solvents such as N-alkylpyrrolidones Oils and fats such as coconut oil, soybean oil, and rapeseed oil; and water.
界面活性剤としては、例えば、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン樹肪酸エステル、ポリオキシエチレン脂肪酸ジエステル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンジアルキルフェニルエーテル、ポリオキシエチレンアルキルフェニルエーテル／ホルマリン縮合物、ポリオキシエチレン／ポリオキシプロピレンブロックポリマー、アルキルポリオキシエチレン／ポリオキシプロピレンブロックポリマーエーテル、アルキルフェニルポリオキシエチレン／ポリオキシプロピレンブロックポリマーエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンビスフェニルエーテル、ポリオキシエチレンベンジルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンエーテル型シリコン、エステル型シリコン、フッ素系界面活性剤などのノニオン性界面活性剤、アルキルサルフェート、ポリオキシエチレンアルキルエーテルサルフェート、ポリオキシエチレンアルキルフェニルエーテルサルフェート、ポリオキシエチレンベンジルフェニルエーテルサルフェート、ポリオキシエチレン／ポリオキシプロピレンブロックポリマーサルフェート、パラフィンスルホネート類、ＡＯＳ類、ジアルキルスルホサクシネート類、アルキルベンゼンスルホネート類、ナフタレンスルホネート類、ナフタレンスルホネート／ホルマリン縮合物類、アルキルジフェニルエーテルジスルホネート類、リグニンスルホネート類、ポリオキシエチレンアルキルフェニルエーテルスルホネート類、ポリオキシエチレンアルキルエーテルスルホコハク酸ハーフエステル類、脂肪酸塩類、Ｎ−メチル−脂肪酸サルコシネート類、樹脂酸塩類、ポリオキシエチレンアルキルエーテルホスフェート類、ポリオキシエチレンアルキルフェニルエーテルホスフェート類、ポリオキシエチレンベンジル化フェニルエーテルホスフェート類、ポリオキシエチレン／ポリオキシプロピレンブロックポリマーホスフェート類、レシチン類、アルキルホスフェート類、アルキルトリメチルアンモニウムクロライド類、メチル／ポリオキシエチレンアルキルアンモニウムクロライド類、アルキルＮ−メチル−ピリジニウムブロマイド類、アルキルメチル化アンモニウムクロライド類、アルキルペンタメチルプロピレンジアミンジクロライド類、アルキルジメチルベンザルコニウムクロライド類、ベンゼトニウムクロライド類、ジアルキルジアミノエチルベタイン類、およびアルキルジメチルベンジルベタイン類などが挙げられる。 Examples of the surfactant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid diester, polyoxyethylene castor oil, Polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether / formalin condensate, polyoxyethylene / polyoxypropylene block polymer, alkyl poly Oxyethylene / polyoxypropylene block polymer ether, alkylphenyl polyoxyethylene / polyoxypropylene block Polymer ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene bisphenyl ether, polyoxyethylene benzyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene ether type silicon, ester type silicon, fluorine-based interface Nonionic surfactants such as activators, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene benzyl phenyl ether sulfates, polyoxyethylene / polyoxypropylene block polymer sulfates, paraffin sulfonates , AOSs, dialkylsulfosuccinates, alkylbenzenesulfonates , Naphthalene sulfonates, naphthalene sulfonate / formalin condensates, alkyl diphenyl ether disulfonates, lignin sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, polyoxyethylene alkyl ether sulfosuccinic acid half esters, fatty acid salts, N-methyl- Fatty acid sarcosinates, resin acid salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, polyoxyethylene benzylated phenyl ether phosphates, polyoxyethylene / polyoxypropylene block polymer phosphates, lecithins, Alkyl phosphates, alkyl trimethyl ammonium chlorides, methyl / polyoxyethyl Lenalkylammonium chlorides, alkyl N-methyl-pyridinium bromides, alkylmethylated ammonium chlorides, alkylpentamethylpropylenediamine dichlorides, alkyldimethylbenzalkonium chlorides, benzethonium chlorides, dialkyldiaminoethylbetaines, and alkyls Examples thereof include dimethylbenzyl betaines.
補助剤としては、例えば、イソプロピルホスフェイト、カルボキシメチルセルロース、ＰＶＡ、トリポリリン酸ソーダ、ヘキサメタリン酸ソーダ、キサンタンガム、グアーガム、カルボキシメチルセルロース、安息香酸ナトリウム、ソルビン酸カリウム、パラヒドロキシ安息香酸エステル、１，２−ベンツチアゾリン−３−オン、エチレングリコール、ジエチレングリコール、プロピレングリコール、ポリビニールプロピドン、尿素、ヘキサメチレンテトラミン、酸化防止剤、紫外線吸収剤、ゼオライト、生石灰、酸化マグネシウム、疎水性高沸点溶剤、ポリアクリル酸ソーダ、アルギン酸、クラフトリグニン、メタクリル酸とビニールプロピドンとの共重合物、グリセリン、ソルビトール、および水膨潤性高分子化合物などが挙げられる。 Examples of the adjuvant include isopropyl phosphate, carboxymethyl cellulose, PVA, sodium tripolyphosphate, sodium hexametaphosphate, xanthan gum, guar gum, carboxymethyl cellulose, sodium benzoate, potassium sorbate, parahydroxybenzoate, 1,2-benz Thiazolin-3-one, ethylene glycol, diethylene glycol, propylene glycol, polyvinyl propidone, urea, hexamethylenetetramine, antioxidant, UV absorber, zeolite, quicklime, magnesium oxide, hydrophobic high boiling point solvent, sodium polyacrylate , Alginic acid, kraft lignin, a copolymer of methacrylic acid and vinyl propidone, glycerin, sorbitol, and a water-swellable polymer compound.
上記の担体、界面活性剤、分散剤、および補助剤は、その各群内および各群間から２種以上選択してそれらを組み合わせて使用してもよい。 Two or more of the above carriers, surfactants, dispersants, and adjuvants may be selected from within each group and between each group and used in combination.
本発明による殺菌性組成物において、式（１）の化合物またはその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物とは、その合計量（有効成分量）が、該殺菌性組成物１００重量部中に、０．１〜９０重量部、好ましくは１〜７０重量部、の割合となるように配合されていればよい。 In fungicidal composition according to the invention, the compound or its acid addition salt of formula (1), and at least one compound selected from strobilurin fungicides, the total amount (active ingredient amount), the sterilization 100 parts by weight of the composition may be blended so as to have a ratio of 0.1 to 90 parts by weight, preferably 1 to 70 parts by weight.
該有効成分量は、該殺菌性組成物の製剤形態、適用方法、使用環境、およびその他の条件を考慮して適宜選択することができる。例えば、該殺菌性組成物が水和剤形態である場合には５〜５０重量％、好ましくは１０〜３０重量％であり、該殺菌性組成物が粉剤形態である場合には０．５〜５．０重量％、好ましくは１．０〜２．０重量％である。 The amount of the active ingredient can be appropriately selected in consideration of the preparation form of the bactericidal composition, the application method, the use environment, and other conditions. For example, when the bactericidal composition is in the form of a wettable powder, it is 5 to 50% by weight, preferably 10 to 30% by weight. When the bactericidal composition is in the form of a powder, 0.5 to 5.0% by weight, preferably 1.0-2.0% by weight.
本発明による殺菌性組成物において、式（１）の化合物またはその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物との配合比は、２：５０〜５０：２の範囲であり、好ましくは１：１０〜１０：１の範囲である。 In the bactericidal composition according to the present invention, the compounding ratio of the compound of formula (1) or an acid addition salt thereof and at least one compound selected from the strobilurin fungicides ranges from 2:50 to 50: 2. And preferably in the range of 1:10 to 10: 1.
本発明による殺菌性組成物を使用する場合には、そのまま直接使用してもよいが、必要に応じて水などの希釈液で希釈して、処理すべき領域に散布、混和、水面施用、浸漬などの処理に付すことができる。そのような処理は、具体的には、例えば、植物体自体への適用（茎葉散布）、育苗箱への適用（育苗箱施用）、土壌への適用（土壌混和もしくは側条施用）、田面水への適用（水面施用もしくは本田適用）、または種子への適用（種子処理）が挙げられる。 When using the bactericidal composition according to the present invention, it may be used directly as it is, but if necessary, dilute with a diluent such as water and spray, mix, apply to the surface of water, immerse in the area to be treated. It can be attached to such processing. Specifically, such treatment includes, for example, application to the plant body itself (stem and foliage application), application to a seedling box (application of a seedling box), application to soil (soil mixing or side application), Tamizu Application to water (water surface application or Honda application), or application to seed (seed treatment).
本発明の別の態様によれば、本発明による殺菌性組成物の有効量を、処理すべき領域に適用することを含んでなる、イネ病害の防除方法が提供される。ここで、「処理すべき領域」とは、イネ病害の防除のために、本発明による殺菌性組成物を使用して処理することが必要とされる領域のことをいい、例えば、イネ植物体、育苗箱、土壌、田面水、または種子が挙げられる。好ましくは、処理すべき領域は、イネ植物体、土壌、または田面水である。 According to another aspect of the present invention there is provided a method for controlling rice diseases comprising applying an effective amount of a bactericidal composition according to the present invention to the area to be treated. Here, the “region to be treated” refers to a region that needs to be treated using the bactericidal composition according to the present invention for controlling rice diseases, for example, a rice plant body. , Nursery boxes, soil, paddy water, or seeds. Preferably, the area to be treated is rice plant, soil, or rice field water.
本発明による殺菌性組成物の使用量は、その使用環境、対象となる植物の生育状態、有効成分の混合比、製剤形態、施用時期、施用方法、防除対象病害の種類に応じて適宜変更可能であるが、通常は１０アール当たりの有効成分量が１〜１，５００ｇ、好ましくは１０〜１５０ｇとなるような量である。例えば、イネ植物体に対して該殺菌性組成物を適用する場合には、その使用量は、有効成分量が１０アール当たり５〜５００ｇ、好ましくは１０〜１００ｇとなるような量である。 The amount of the bactericidal composition according to the present invention can be appropriately changed according to the environment in which it is used, the growth state of the target plant, the mixing ratio of the active ingredients, the preparation form, the application time, the application method, and the type of the disease to be controlled. However, it is usually such an amount that the amount of active ingredient per 10 are is 1-1,500 g, preferably 10-150 g. For example, when the fungicidal composition is applied to a rice plant body, the amount used thereof is such that the amount of the active ingredient is 5 to 500 g, preferably 10 to 100 g per 10 ares.
本発明による殺菌性組成物は他の殺菌剤、殺虫剤、殺ダニ剤、除草剤、植物成長調節剤、肥料等と混合して用いてもよい。 The fungicidal composition according to the present invention may be used by mixing with other fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and the like.
本発明による殺菌性組成物は、前記したように予め調製して製剤化しておいて用いるのが通常であるが、該組成物中の有効成分である、式（１）の化合物またはその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物とを、それぞれ単独で含んでなる製剤形態を調製しておき、使用する際に、これらをその場で混合して用いてもよい。 The bactericidal composition according to the present invention is usually prepared and formulated in advance as described above, and is used, but the compound of formula (1) or an acid addition thereof, which is an active ingredient in the composition A preparation form comprising a salt and at least one compound selected from strobilurin-based fungicides alone may be prepared, and when used, these may be mixed and used on the spot. .
よって本発明の別の態様によれば、式（１）の化合物またはその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物とを含んでなる、組み合わせ物が提供される。 Thus according to another aspect of the present invention there is provided a combination comprising a compound of formula (1) or an acid addition salt thereof and at least one compound selected from strobilurin fungicides .
本発明の別の好ましい態様によれば、前記組み合わせ物において、式（１）の化合物またはその酸付加塩は、それを有効成分として含んでなる第１の組成物として提供され、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物は、それを有効成分として含んでなる第２の組成物として提供される。この場合、第１の組成物と第２の組成物は、前記した殺菌性組成物の場合と同様に、適当な担体または補助剤を併用して任意の剤型であることができる。該組み合わせ物は、薬剤セットのような形態で提供されてもよい。 According to another preferred embodiment of the present invention, in the combination, the compound of formula (1) or an acid addition salt thereof is provided as a first composition comprising it as an active ingredient, and a strobilurin fungicide At least one compound selected from is provided as a second composition comprising it as an active ingredient. In this case, the first composition and the second composition can be in any dosage form in combination with an appropriate carrier or auxiliary agent, as in the case of the bactericidal composition described above. The combination may be provided in the form of a drug set.
本発明の別の態様によれば、水稲病害の防除剤を製造するため、前記組み合わせ物の使用が提供される。ここで「水稲病害の防除剤」は、本発明による殺菌性組成物からなるものである。 According to another aspect of the present invention, there is provided use of the combination for producing a paddy rice disease control agent. Here, the “paddy rice disease control agent” comprises the bactericidal composition according to the present invention.
本発明のさらに別の態様によれば、イネ病害の防除方法であって、式（１）の化合物またはその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物とを、処理すべき領域に同時または別々に適用することを含んでなる方法が提供される。 According to still another aspect of the present invention, there is provided a method for controlling a rice disease, comprising treating a compound of formula (1) or an acid addition salt thereof and at least one compound selected from strobilurin fungicides. A method is provided that comprises applying simultaneously or separately to the area to be performed.
この方法において、「同時に」適用することには、式（１）の化合物またはそのその酸付加塩と、ストロビルリン系殺菌剤から選択される少なくとも１種の化合物とを処理すべき領域に適用する前に混合して、その混合物を適用することも包含される。「別々に」適用することには、それらを予め混合することなく、式（１）の化合物またはその酸付加塩を他方の成分より先に適用すること、および式（１）の化合物またはその酸付加塩を他方の成分より後に適用することが包含される。 In this method, to apply “simultaneously”, before applying the compound of formula (1) or its acid addition salt and at least one compound selected from strobilurin fungicides to the area to be treated. And mixing the mixture and applying the mixture. Applying “separately” includes applying the compound of formula (1) or its acid addition salt prior to the other component without premixing them, and the compound of formula (1) or its acid Application of the addition salt after the other component is included.
本発明のさらに別の好ましい態様によれば、
(A) 式（１）の化合物またはその酸付加塩を有効成分として含んでなる、第１の組成物と、
(B) ストロビルリン系殺菌剤から選択される少なくとも１種の化合物を有効成分として含んでなる、第２の組成物と
を処理すべき領域に適用することを含んでなるイネ病害の防除方法が提供される。
According to still another preferred embodiment of the present invention,
(A) a first composition comprising a compound of formula (1) or an acid addition salt thereof as an active ingredient;
(B) A method for controlling rice diseases comprising applying a second composition comprising at least one compound selected from strobilurin fungicides as an active ingredient to an area to be treated is provided. Is done.
以下本発明を以下の実施例によって詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto.
式（１）の化合物の製造
下記表１に示されるような置換基を有する式（１）の化合物（化合物１〜１１）を製造した。
化合物１〜１１の製造は、具体的には下記のような手順にしたがって行った。 Specifically, the compounds 1 to 11 were produced according to the following procedure.
４−ｔ−ブチル−２−フルオロアニリンの製造
アセトニトリル（２００ｍｌ）にSELECTFLUOR（Aldrich Chemical Company Inc製）（１−クロロ−メチル−４−フルオロ−１，４−ジアゾニアビシクロ［２，２，２］オクタン−ビス−テトラフルオロボレート）（１５ｇ）を７０℃で３０分加熱し、溶解させた。得られた反応液を６０℃まで冷却し、これに４−ｔ−ブチル−アセトアニリド（５．７ｇ）を加えた。１００℃で１時間撹拌し、放冷後、該反応液を水（２００ｍｌ）に加え、これを酢酸エチルを用いて抽出した（１００ｍｌ、２回）。酢酸エチル層を飽和食塩水で洗浄し、無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００（和光純薬工業社製），溶出溶媒ｎ−ヘキサン−酢酸エチル（１０：１））を用いて精製し、４−ｔ−ブチル−２−フルオロ−アセトアニリド（３．０６ｇ）を得た。この４−ｔ−ブチル−２−フルオロ−アセトアニリド（３．６７ｇ）を、エタノール（３０ｍｌ）と濃塩酸（１５ｍｌ）の混合液中に加え、これを９５℃において２時間撹拌した。この反応液を放冷後、水にあけ、飽和炭酸水素ナトリウム水溶液で中和した後、酢酸エチルを用いて抽出した。酢酸エチル層を飽和炭酸水素ナトリウム水溶液および飽和食塩水を用いて洗浄し、無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去して、４−ｔ−ブチル−２−フルオロアニリン（３．４９ｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．０１（１Ｈ，ｄｄ）， ６．９５（１Ｈ，ｄｄ）， ６．７３（１Ｈ，ｍ）， １．２８（９Ｈ，ｓ）
Preparation of 4-t-butyl-2-fluoroaniline SELECTFLUOR (Aldrich Chemical Company Inc) (1-chloro-methyl-4-fluoro-1,4-diazoniabicyclo [2,2,2]) in acetonitrile (200 ml) Octane-bis-tetrafluoroborate) (15 g) was heated at 70 ° C. for 30 minutes to dissolve. The obtained reaction liquid was cooled to 60 ° C., and 4-t-butyl-acetanilide (5.7 g) was added thereto. After stirring at 100 ° C. for 1 hour and allowing to cool, the reaction mixture was added to water (200 ml) and extracted with ethyl acetate (100 ml, twice). The ethyl acetate layer was washed with saturated brine and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting crude product was purified using silica gel chromatography (Wakogel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), elution solvent n-hexane-ethyl acetate (10: 1)) to give 4-t-butyl- 2-Fluoro-acetanilide (3.06 g) was obtained. This 4-t-butyl-2-fluoro-acetanilide (3.67 g) was added to a mixture of ethanol (30 ml) and concentrated hydrochloric acid (15 ml), and this was stirred at 95 ° C. for 2 hours. The reaction mixture was allowed to cool, poured into water, neutralized with saturated aqueous sodium hydrogen carbonate solution, and extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 4-t-butyl-2-fluoroaniline (3 .49 g) was obtained. The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.01 (1H, dd), 6.95 (1H, dd), 6.73 (1H, m), 1.28 (9H, s)
化合物１： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ヒドロキシキノリン
上記のプロセスに従って得られた４−ｔ−ブチル−２−フルオロアニリン（４．７９ｇ）と２−メチル−アセト酢酸エチル（４．９６ｇ）とを、トリフルオロボロンエーテレート（０．３ｍｌ）の存在下、トルエン中（６０ｍｌ）において３時間還流し、反応液を得た。得られた反応液を飽和炭酸水素ナトリウム水溶液および飽和食塩水を用いて洗浄し、無水硫酸ナトリウム上で乾燥させた後、減圧下においてその溶媒を留去した。得られた反応生成物をジフェニルエーテル（８０ｍｌ）中において１時間還流し、放冷させた後、析出した生成物を減圧下で濾取し、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ヒドロキシキノリン（化合物１）（１．６６ｇ）を得た。この化合物の重ＤＭＳＯ（ジメチルスルホキシド）中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： １１．２７（１Ｈ，ｂｒ．ｓ）， ７．８３（１Ｈ，ｓ）， ７．５９（１Ｈ，ｂｒ．ｄ）， ２．４１（３Ｈ，ｓ）， １．９６（３Ｈ，ｓ）， １．３１（９Ｈ，ｓ）
Compound 1: 2,3-Dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline 4-tert-butyl-2-fluoroaniline (4.79 g) obtained according to the above process and 2-methyl- Ethyl acetoacetate (4.96 g) was refluxed in toluene (60 ml) in the presence of trifluoroboron etherate (0.3 ml) for 3 hours to obtain a reaction solution. The obtained reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting reaction product was refluxed in diphenyl ether (80 ml) for 1 hour and allowed to cool, and then the precipitated product was collected by filtration under reduced pressure, and 2,3-dimethyl-6-t-butyl-8- Fluoro-4-hydroxyquinoline (Compound 1) (1.66 g) was obtained. The 1 H-NMR data of this compound in heavy DMSO (dimethyl sulfoxide) is shown below.
δ (ppm): 11.27 (1H, br.s), 7.83 (1H, s), 7.59 (1H, br. d), 2.41 (3H, s), 1.96 (3H) , S), 1.31 (9H, s)
化合物２： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−アセチルオキシキノリン
化合物１（５０ｍｇ）を、無水酢酸（３ｍｌ）中において、１２０℃で３時間撹拌して反応液を得た。得られた反応液から減圧下において無水酢酸を留去した。得られた残渣を酢酸エチルで溶解させ、飽和炭酸水素ナトリウム水溶液および飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（５：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−アセチルオキシキノリン（化合物２）（３５．７ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４３（１Ｈ，ｄｄ）， ７．３７（１Ｈ，ｄ）， ２．７８（３Ｈ，ｓ）， ２．５１（３Ｈ，ｓ）， ２．２６（３Ｈ，ｓ）， １．３８（９Ｈ，ｓ）
Compound 2: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-acetyloxyquinoline Compound 1 (50 mg) was stirred in acetic anhydride (3 ml) at 120 ° C. for 3 hours to prepare a reaction solution. Obtained. Acetic anhydride was distilled off from the resulting reaction solution under reduced pressure. The obtained residue was dissolved in ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (5: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. Fluoro-4- acetyloxyquinoline (Compound 2) (35.7 mg) was obtained. The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.43 (1H, dd), 7.37 (1H, d), 2.78 (3H, s), 2.51 (3H, s), 2.26 (3H, s), 1.38 (9H, s)
化合物３： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−プロピオニルオキシキノリン
６０％水素化ナトリウム（２０ｍｇ）をテトラヒドロフラン（３ｍｌ）に懸濁し、そこに、氷冷下、化合物１（１２４ｍｇ）を加えて、３０分間撹拌した。これにプロピオニルクロリド（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−プロピオニルオキシキノリン（２１ｍｇ）（化合物３）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４２（１Ｈ，ｄｄ）， ７．３６（１Ｈ，ｄ）， ２．８１（２Ｈ，ｑ）， ２．７５（３Ｈ，ｓ）， ２．２５（３Ｈ，ｓ）， １．４３（３Ｈ，ｔ）， １．３７（９Ｈ，ｓ）
Compound 3: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-propionyloxyquinoline 60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 ml), and the compound 1 was added thereto under ice-cooling. (124 mg) was added and stirred for 30 minutes. To this was further added propionyl chloride (200 μl) and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. to obtain a fluoro-4-propionyl-oxy quinoline (21 mg) (compound 3). The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.42 (1H, dd), 7.36 (1H, d), 2.81 (2H, q), 2.75 (3H, s), 2.25 (3H, s), 1.43 (3H, t), 1.37 (9H, s)
化合物４： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ブチリルオキシキノリン
６０％水素化ナトリウム（２０ｍｇ）をテトラヒドロフラン（３ｍｌ）に懸濁し、そこに、氷冷下、化合物１（１２４ｍｇ）を加えて、３０分間撹拌した。これにブチリルクロリド（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ブチリルオキシキノリン（化合物４）（６４ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４３（１Ｈ，ｄｄ）， ７．３７（１Ｈ，ｄ）， ２．７６（２Ｈ，ｔ）， ２．７５（３Ｈ，ｓ）， ２．２５（３Ｈ，ｓ）， １．９４（２Ｈ，ｍ）， １．３７（９Ｈ，ｓ）， １．１５（３Ｈ，ｔ）
Compound 4: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-butyryloxyquinoline 60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 ml), and the compound was added under ice cooling. 1 (124 mg) was added and stirred for 30 minutes. To this, butyryl chloride (200 μl) was further added and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. fluoro-4-butyryl-oxy quinoline (compound 4) was obtained (64 mg). The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.43 (1H, dd), 7.37 (1H, d), 2.76 (2H, t), 2.75 (3H, s), 2.25 (3H, s), 1.94 (2H, m), 1.37 (9H, s), 1.15 (3H, t)
化合物５： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−バレリルオキシキノリン
６０％水素化ナトリウム（２０ｍｇ）をテトラヒドロフラン（３ｍｌ）に懸濁し、そこに、氷冷下、化合物１（１２４ｍｇ）を加えて、３０分間撹拌した。これにバレリルクロリド（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−バレリルオキシキノリン（化合物５）（１２０ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４２（１Ｈ，ｄｄ）， ７．３７（１Ｈ，ｄ）， ２．７８（２Ｈ，ｔ）， ２．７５（３Ｈ，ｓ）， ２．２５（３Ｈ，ｓ）， １．８９（２Ｈ，ｍ）， １．５６（２Ｈ，ｍ）， １．３７（９Ｈ，ｓ）， １．０３（３Ｈ，ｔ）
Compound 5: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-valeryloxyquinoline 60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 ml), and the compound was added under ice cooling. 1 (124 mg) was added and stirred for 30 minutes. Valeryl chloride (200 μl) was further added thereto and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. Fluoro-4 - valeryloxyquinoline (Compound 5) (120 mg) was obtained. The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.42 (1H, dd), 7.37 (1H, d), 2.78 (2H, t), 2.75 (3H, s), 2.25 (3H, s), 1.89 (2H, m), 1.56 (2H, m), 1.37 (9H, s), 1.03 (3H, t)
化合物６： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−メトキシカルボニルオキシキノリン
６０％水素化ナトリウム（２０ｍｇ）をテトラヒドロフラン（３ｍｌ）に懸濁し、そこに、氷冷下、化合物１（１２４ｍｇ）を加えて、３０分間撹拌した。これにクロロギ酸メチル（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−メトキシカルボニルオキシキノリン（化合物６）（１００ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４５（１Ｈ，ｂｒ．ｓ）， ７．４３（１Ｈ，ｄｄ）， ４．００（３Ｈ，ｓ）， ２．７６（３Ｈ，ｓ）， ２．３１（３Ｈ，ｓ）， １．３８（９Ｈ，ｓ）
Compound 6: 2,3-Dimethyl-6-tert-butyl-8-fluoro-4-methoxycarbonyloxyquinoline 60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 ml), and the resulting solution was cooled under ice-cooling. 1 (124 mg) was added and stirred for 30 minutes. To this, methyl chloroformate (200 μl) was further added and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. fluoro-4-methoxycarbonyloxy-quinoline (compound 6) was obtained (100 mg). The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.45 (1H, br.s), 7.43 (1H, dd), 4.00 (3H, s), 2.76 (3H, s), 2.31 (3H, s) ), 1.38 (9H, s)
化合物７： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−エトキシカルボニルオキシキノリン
６０％水素化ナトリウム（６０ｍｇ）をテトラヒドロフラン（１０ｍｌ）に懸濁し、そこに、氷冷下、化合物１（２００ｍｇ）を加えて、３０分間撹拌した。これにクロロギ酸エチル（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−エトキシカルボニルオキシキノリン（化合物７）（２２０ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４５（１Ｈ，ｂｒ．ｓ）， ７．４３（１Ｈ，ｄｄ）， ４．４０（２Ｈ，ｑ，Ｊ＝６．７Ｈｚ）， ２．３２（３Ｈ，ｓ，）， ２．０４（３Ｈ，ｓ）， １．４４（３Ｈ，ｔ）， １．３８（９Ｈ，ｓ）
Compound 7: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-ethoxycarbonyloxyquinoline 60% sodium hydride (60 mg) was suspended in tetrahydrofuran (10 ml), and the resulting solution was cooled under ice cooling. 1 (200 mg) was added and stirred for 30 minutes. To this, ethyl chloroformate (200 μl) was further added and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. fluoro-4-ethoxycarbonyl-oxy quinoline (compound 7) was obtained (220 mg). The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.45 (1H, br.s), 7.43 (1H, dd), 4.40 (2H, q, J = 6.7 Hz), 2.32 (3H, s,), 2.04 (3H, s), 1.44 (3H, t), 1.38 (9H, s)
化合物８： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ノルマルプロポキシカルボニルオキシキノリン
６０％水素化ナトリウム（２０ｍｇ）をテトラヒドロフラン（３ｍｌ）に懸濁し、そこに、氷冷下、化合物１（１２４ｍｇ）を加えて、３０分間撹拌した。これにクロロギ酸ノルマルプロピル（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液を飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ノルマルプロポキシカルボニルオキシキノリン（化合物８）（９６ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４５（１Ｈ，ｂｒ．ｓ）， ７．４３（１Ｈ，ｄｄ）， ４．３５（２Ｈ，ｔ，Ｊ＝６．７Ｈｚ）， ２．７５（３Ｈ，ｓ）， ２．３１（３Ｈ，ｓ）， １．８２（２Ｈ，ｍ）， １．３８（９Ｈ，ｓ）， １．０４（３Ｈ，ｔ）
Compound 8: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-normalpropoxycarbonyloxyquinoline 60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 ml), and the resulting mixture was ice-cooled. Compound 1 (124 mg) was added and stirred for 30 minutes. To this, normal propyl chloroformate (200 μl) was further added and stirred for 3 hours. The obtained reaction solution was poured into ice water, extracted with ethyl acetate, and the ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. Fluoro-4 - normalpropoxycarbonyloxyquinoline (Compound 8) (96 mg) was obtained. The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.45 (1H, br.s), 7.43 (1H, dd), 4.35 (2H, t, J = 6.7 Hz), 2.75 (3H, s), 2 .31 (3H, s), 1.82 (2H, m), 1.38 (9H, s), 1.04 (3H, t)
化合物９： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ノルマルブトキシカルボニルオキシキノリン
６０％水素化ナトリウム（６０ｍｇ）をテトラヒドロフラン（１０ｍｌ）に懸濁し、そこに、氷冷下、化合物１（２００ｍｇ）を加えて、３０分間撹拌した。これにクロロギ酸ノルマルブチル（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−ノルマルブトキシカルボニルオキシキノリン（化合物９）（１４２ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４５（１Ｈ，ｄ）， ７．４３（１Ｈ，ｄｄ）， ４．３５（２Ｈ，ｔ）， ２．７５（３Ｈ，ｓ）， ２．３２（３Ｈ，ｓ）， １．７７（２Ｈ，ｍ）， １．４８（２Ｈ，ｍ）， １．３８（９Ｈ，ｓ）， ０．９９（３Ｈ，ｔ）
Compound 9: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-normalbutoxycarbonyloxyquinoline 60% sodium hydride (60 mg) was suspended in tetrahydrofuran (10 ml), and the resulting mixture was ice-cooled. Compound 1 (200 mg) was added and stirred for 30 minutes. To this, normal butyl chloroformate (200 μl) was further added and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. Fluoro-4 - normalbutoxycarbonyloxyquinoline (Compound 9) (142 mg) was obtained. The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.45 (1H, d), 7.43 (1H, dd), 4.35 (2H, t), 2.75 (3H, s), 2.32 (3H, s), 1.77 (2H, m), 1.48 (2H, m), 1.38 (9H, s), 0.99 (3H, t)
化合物１０： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−メトキシアセチルオキシキノリン
６０％水素化ナトリウム（１６５ｍｇ）をテトラヒドロフラン（１０ｍｌ）に懸濁し、そこに、氷冷下、化合物１（６８０ｍｇ）を加えて、３０分間撹拌した。これにメトキシアセチルクロリド（２００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−メトキシアセチルオキシキノリン（化合物１０）（３９０ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４２（１Ｈ，ｄｄ）， ７．３５（１Ｈ，ｄ）， ４．５１（２Ｈ，ｓ）， ３．６２（３Ｈ，ｓ）， ２．７５（３Ｈ，ｓ）， ２．２６（３Ｈ，ｓ）， １．３７（９Ｈ，ｓ）
Compound 10: 2,3-Dimethyl-6-tert-butyl-8-fluoro-4-methoxyacetyloxyquinoline 60% sodium hydride (165 mg) was suspended in tetrahydrofuran (10 ml), and the compound was added to the solution under ice cooling. 1 (680 mg) was added and stirred for 30 minutes. Methoxyacetyl chloride (200 μl) was further added thereto, and the mixture was stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. fluoro-4-methoxy acetyloxy quinoline (compound 10) was obtained (390 mg). The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.42 (1H, dd), 7.35 (1H, d), 4.51 (2H, s), 3.62 (3H, s), 2.75 (3H, s), 2.26 (3H, s), 1.37 (9H, s)
化合物１１： ２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−アセトキシアセチルオキシキノリン
６０％水素化ナトリウム（４４ｍｇ）をテトラヒドロフラン（１０ｍｌ）に懸濁し、そこに、氷冷下、化合物１（２００ｍｇ）を加えて、３０分間撹拌した。これにアセトキシアセチルクロリド（１００μｌ）をさらに加えて３時間撹拌した。得られた反応液を氷水にあけ、これを酢酸エチルで抽出し、酢酸エチル層を飽和炭酸水素ナトリウム水溶液と飽和食塩水を用いて洗浄し、次いで無水硫酸ナトリウム上で乾燥させた後、減圧下溶媒を留去した。得られた粗生成物をシリカゲルクロマトグラフィー（ワコーゲルＣ−２００，溶出溶媒ｎ−ヘキサン−酢酸エチル（３：１））にて精製して、２，３−ジメチル−６−ｔ−ブチル−８−フルオロ−４−アセトキシアセチルオキシキノリン（化合物１１）（１４０ｍｇ）を得た。この化合物の重クロロホルム中における１Ｈ−ＮＭＲデータを以下に示す。
δ（ｐｐｍ）： ７．４３（１Ｈ，ｄｄ）， ７．４２（１Ｈ，ｂｒ．ｓ）， ５．０２（２Ｈ，ｓ）， ２．７５（３Ｈ，ｓ）， ２．２７（３Ｈ，ｓ）， ２．２３（３Ｈ，ｓ）， １．４０（９Ｈ，ｓ）
Compound 11: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-acetoxyacetyloxyquinoline 60% sodium hydride (44 mg) was suspended in tetrahydrofuran (10 ml), and the compound was added under ice cooling. 1 (200 mg) was added and stirred for 30 minutes. Acetoxyacetyl chloride (100 μl) was further added thereto and stirred for 3 hours. The obtained reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate, and then under reduced pressure. The solvent was distilled off. The obtained crude product was purified by silica gel chromatography (Wakogel C-200, elution solvent n-hexane-ethyl acetate (3: 1)) to obtain 2,3-dimethyl-6-tert-butyl-8-. Fluoro-4 - acetoxyacetyloxyquinoline (Compound 11) (140 mg) was obtained. The 1 H-NMR data of this compound in deuterated chloroform is shown below.
δ (ppm): 7.43 (1H, dd), 7.42 (1H, br.s), 5.02 (2H, s), 2.75 (3H, s), 2.27 (3H, s) ), 2.23 (3H, s), 1.40 (9H, s)
製剤例
製剤例１： 水和剤
下記成分を均一に粉砕して、水和剤を得た。
化合物２ ２０ 重量部
アゾキシストロビン ２０ 重量部
珪藻土 ２８ 重量部
ホワイトカーボン（商品名）（塩野義製薬会社製）
１３ 重量部
ポリオキシエチレンラウリルエーテル １２ 重量部
リグニンスルホン酸カルシウム ７ 重量部
Formulation example
Formulation example 1: wettable powder The following component was grind | pulverized uniformly and the wettable powder was obtained.
Compound 2 20 parts by weight
20 parts by weight of azoxystrobin
Diatomaceous earth 28 parts by weight
White carbon (trade name) (made by Shionogi Pharmaceutical Co., Ltd.)
13 parts by weight
12 parts by weight of polyoxyethylene lauryl ether
7 parts by weight of calcium lignin sulfonate
製剤例２： 水和剤
下記成分を均一に粉砕して、水和剤を得た。
化合物２ １５ 重量部
アゾキシストロビン ５ 重量部
珪藻土 ４７ 重量部
クレー １０ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
１０ 重量部
ポリオキシエチレンラウリルエーテル ８ 重量部
リグニンスルホン酸カルシウム ５ 重量部
Formulation Example 2: Wettable powder The following ingredients were uniformly ground to obtain a wettable powder.
Compound 2 15 parts by weight
Azoxystrobin 5 parts by weight
Diatomaceous earth 47 parts by weight
10 parts by weight of clay
White carbon (trade name) (made by Shionogi & Co., Ltd.)
10 parts by weight
Polyoxyethylene lauryl ether 8 parts by weight
Calcium lignin sulfonate 5 parts by weight
製剤例３： 水和剤
下記成分を均一に粉砕して、水和剤を得た。
化合物２ ２０ 重量部
アゾキシストロビン １０ 重量部
珪藻土 ４２ 重量部
クレー ５ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
１０ 重量部
ポリオキシエチレンラウリルエーテル ８ 重量部
リグニンスルホン酸カルシウム ５ 重量部
Formulation Example 3: Wettable powder The following ingredients were uniformly ground to obtain a wettable powder.
Compound 2 20 parts by weight
10 parts by weight of azoxystrobin
Diatomaceous earth 42 parts by weight
5 parts by weight of clay
White carbon (trade name) (made by Shionogi & Co., Ltd.)
10 parts by weight
Polyoxyethylene lauryl ether 8 parts by weight
Calcium lignin sulfonate 5 parts by weight
製剤例４： 水和剤
下記成分を均一に粉砕して、水和剤を得た。
化合物２ ２０ 重量部
メトミノストロビン ２０ 重量部
珪藻土 ３７ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
１０ 重量部
ポリオキシエチレンラウリルエーテル ８ 重量部
リグニンスルホン酸カルシウム ５ 重量部
Formulation Example 4: Wettable powder The following ingredients were uniformly ground to obtain a wettable powder.
Compound 2 20 parts by weight
Metominostrobin 20 parts by weight
Diatomaceous earth 37 parts by weight
White carbon (trade name) (made by Shionogi & Co., Ltd.)
10 parts by weight
Polyoxyethylene lauryl ether 8 parts by weight
Calcium lignin sulfonate 5 parts by weight
製剤例５： 水和剤
下記成分を均一に粉砕して、水和剤を得た。
化合物２ １５ 重量部
メトミノストロビン ５ 重量部
珪藻土 ４７ 重量部
クレー １０ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
１０ 重量部
ポリオキシエチレンラウリルエーテル ８ 重量部
リグニンスルホン酸カルシウム ５ 重量部
Formulation Example 5: Wettable powder The following ingredients were uniformly ground to obtain a wettable powder.
Compound 2 15 parts by weight
Metominostrobin 5 parts by weight
Diatomaceous earth 47 parts by weight
10 parts by weight of clay
White carbon (trade name) (made by Shionogi & Co., Ltd.)
10 parts by weight
Polyoxyethylene lauryl ether 8 parts by weight
Calcium lignin sulfonate 5 parts by weight
製剤例６： 水和剤
下記成分を均一に粉砕して、水和剤を得た。
化合物２ ２０ 重量部
メトミノストロビン １０ 重量部
珪藻土 ４２ 重量部
クレー ５ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
１０ 重量部
ポリオキシエチレンラウリルエーテル ８ 重量部
リグニンスルホン酸カルシウム ５ 重量部
Formulation Example 6: Wettable powder The following ingredients were uniformly ground to obtain a wettable powder.
Compound 2 20 parts by weight
Metominostrobin 10 parts by weight
Diatomaceous earth 42 parts by weight
5 parts by weight of clay
White carbon (trade name) (made by Shionogi & Co., Ltd.)
10 parts by weight
Polyoxyethylene lauryl ether 8 parts by weight
Calcium lignin sulfonate 5 parts by weight
製剤例７： 粉剤
下記成分を均一に粉砕して、粉剤を得た。
化合物２ １．２ 重量部
アゾキシストロビン ０．５ 重量部
クレー ９７．１ 重量部
炭酸カルシウム ０．５ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
０．２ 重量部
ドリレスＡ（商品名）（三共株式会社製） ０．５ 重量部
Formulation example 7: Powder The following component was grind | pulverized uniformly and the powder was obtained.
Compound 2 1.2 parts by weight
Azoxystrobin 0.5 parts by weight
97.1 parts by weight of clay
Calcium carbonate 0.5 parts by weight
White carbon (trade name) (made by Shionogi & Co., Ltd.)
0.2 parts by weight
Doriles A (trade name) (manufactured by Sankyo Corporation) 0.5 parts by weight
製剤例８： 粉剤
下記成分を均一に粉砕して、粉剤を得た。
化合物２ １ 重量部
アゾキシストロビン ０．５ 重量部
クレー ９７．１ 重量部
炭酸カルシウム ０．５ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
０．４ 重量部
ドリレスＡ（商品名）（三共株式会社製） ０．５ 重量部
Formulation Example 8: Powder A powder was obtained by uniformly grinding the following components.
Compound 2 1 part by weight
Azoxystrobin 0.5 parts by weight
97.1 parts by weight of clay
Calcium carbonate 0.5 parts by weight
White carbon (trade name) (made by Shionogi & Co., Ltd.)
0.4 parts by weight
Doriles A (trade name) (manufactured by Sankyo Corporation) 0.5 parts by weight
製剤例９： 粉剤
下記成分を均一に粉砕して、粉剤を得た。
化合物２ １．２ 重量部
メトミノストロビン ０．５ 重量部
クレー ９７．１ 重量部
炭酸カルシウム ０．５ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
０．２ 重量部
ドリレスＡ（商品名）（三共株式会社製） ０．５ 重量部
Formulation Example 9: Powder A powder was obtained by uniformly grinding the following components.
Compound 2 1.2 parts by weight
Metominostrobin 0.5 parts by weight
97.1 parts by weight of clay
Calcium carbonate 0.5 parts by weight
White carbon (trade name) (made by Shionogi & Co., Ltd.)
0.2 parts by weight
Doriles A (trade name) (manufactured by Sankyo Corporation) 0.5 parts by weight
製剤例１０： 粉剤
下記成分を均一に粉砕して、粉剤を得た。
化合物２ １ 重量部
メトミノストロビン ０．５ 重量部
クレー ９７．１ 重量部
炭酸カルシウム ０．５ 重量部
ホワイトカーボン（商品名）（塩野義製薬株式会社製）
０．４ 重量部
ドリレスＡ（商品名）（三共株式会社製） ０．５ 重量部
Formulation Example 10: Powder The following components were uniformly pulverized to obtain a powder.
Compound 2 1 part by weight
Metominostrobin 0.5 parts by weight
97.1 parts by weight of clay
Calcium carbonate 0.5 parts by weight
White carbon (trade name) (made by Shionogi & Co., Ltd.)
0.4 parts by weight
Doriles A (trade name) (manufactured by Sankyo Corporation) 0.5 parts by weight
評価試験
試験Ａ： 蔓延前散布によるイネいもち病防除効果（防除適期試験）
プラスチック製バット（３０ｃｍ×５０ｃｍ程度）に培養土を入れ、催芽済みのイネ種籾（品種：コシヒカリ）を播種して、密植栽培したものを用いた。
Evaluation test
Test A: Rice blast control effect by spraying before spreading (control suitable period test)
Cultured soil was put into a plastic vat (about 30 cm × 50 cm), seeded rice seed varieties (variety: Koshihikari) were sowed, and those that were closely planted were used.
該イネをガラス温室内で昼２５℃、夜２０℃の条件下において２週間程度栽培して、３〜４葉期に生育した頃に、あらかじめイネいもち病菌（レース０３７）を接種して発病させておいた罹病葉を、密植した該イネの上に設置した。これを２４時間過湿条件下に置いて菌の接種を行った。該イネを再びガラス温室内に戻し、７〜８日後に病斑を確認した後に、第１回薬剤散布を行った。供試薬液は１０％アセトン水（展着剤としてネオエステリン（商品名）（クミアイ化学工業株式会社製）の５，０００倍液を加用したもの）用いて所定濃度に調整し、スプレーガンを用いてバットあたり１５ｍｌ散布した。第２回薬剤散布を行う場合には、さらに６〜７日後に第１回散布の場合と第２回薬剤散布を同様にして行った。 The rice is cultivated in a glass greenhouse for about 2 weeks under the conditions of 25 ° C in the daytime and 20 ° C in the nighttime. When the rice grows in the 3-4 leaf stage, it is inoculated with rice blast fungus (race 037) in advance. The diseased leaves were placed on the densely planted rice. This was placed under superhumid conditions for 24 hours to inoculate the bacteria. The rice was returned to the glass greenhouse again, and after spotting the lesion 7 to 8 days later, the first drug spraying was performed. The reagent solution was adjusted to a predetermined concentration using 10% acetone water (neoesterin (trade name) (made by Kumiai Chemical Industry Co., Ltd.) 5,000 times solution added as a spreading agent) and spray gun. Was sprayed with 15 ml per vat. In the case of performing the second drug spraying, the second drug spraying was performed in the same manner as in the case of the first spraying after 6 to 7 days.
薬剤散布後は、イネをガラス温室内で管理し、１〜２日間隔で過湿条件下に２４時間おいて発病、蔓延を促した。 After spraying the chemicals, rice was managed in a glass greenhouse, and the disease and spread were promoted at intervals of 1-2 days under superhumid conditions for 24 hours.
最終的な薬剤散布の１０日後に、１バットあたり４０株について、最上位から一枚下の葉身上の病斑面積を観察し、処理区の病斑面積率を求めた。得られた結果と、無処理区の場合に得られた結果とから下記式にしたがって、各試験薬剤についての防除価を算出した。 Ten days after the final drug spraying, the lesion area on the leaf blades from the top was observed for 40 strains per bat, and the lesion area ratio of the treated area was determined. From the results obtained and the results obtained in the case of the untreated section, the control value for each test drug was calculated according to the following formula.
防除価＝［１−（処理区の病斑面積率／無処理区の病斑面積率）］×１００
試験薬剤の予防効果および残効性は、薬剤処理後に所定の日数を経過した時点で、病斑面積率が増加するか否かにより判定できる。よって、最終的に得られた防除価が高くなるか否かにより、予防効果および残効性を判定した。
Control value = [1- (Lesion area ratio of treated area / Lesion area ratio of untreated area)] × 100
The preventive effect and residual effect of the test drug can be determined by whether or not the lesion area rate increases when a predetermined number of days have elapsed after the drug treatment. Therefore, the preventive effect and the residual effect were determined depending on whether or not the finally obtained control value was high.
なお試験は、下記表Ａ１〜表Ａ３の各表にある薬剤を１グループとして、各グループ毎に行った。また薬剤散布は、１回または２回行った。 In addition, the test was conducted for each group with the drugs in each table of the following Tables A1 to A3 as one group. Moreover, the chemical spraying was performed once or twice.
結果は表Ａ１〜表Ａ３に示されるとおりであった。
試験Ｂ： 蔓延後散布によるイネいもち病防除効果（散布遅れ試験）
プラスチック製バット（３０ｃｍ×５０ｃｍ程度）に培養土を入れ、催芽済みのイネ種籾（品種：コシヒカリ）を播種して、密植栽培したものを用いた。
Test B: Effect of rice blast control by spreading after spreading (spraying delay test)
Cultured soil was put into a plastic vat (about 30 cm × 50 cm), seeded rice seed varieties (variety: Koshihikari) were sowed, and those that were closely planted were used.
該イネをガラス温室内で昼２５℃、夜２０℃の条件下において２週間程度栽培して、３〜４葉期に生育した頃に、あらかじめイネいもち病菌（レース０３７）を接種して発病させておいた罹病葉を、密植した該イネの上に設置した。これを２４時間過湿条件下に置いて菌の接種を行った。該イネを再びガラス温室内に戻し、７〜８日後に病斑を確認した。その後、再び２４時間過湿条件下に置いて第２次伝染を促し、バット内でイネいもち病を蔓延させるようにした。蔓延を促してから３〜４日程度経過した後、極小さな第２次病斑が確認できるようになってから、第１回の薬剤散布を行った。 The rice is cultivated in a glass greenhouse for about 2 weeks under the conditions of 25 ° C in the daytime and 20 ° C in the nighttime. When the rice grows in the 3-4 leaf stage, it is inoculated with rice blast fungus (race 037) in advance. The diseased leaves were placed on the densely planted rice. This was placed under superhumid conditions for 24 hours to inoculate the bacteria. The rice was returned to the glass greenhouse again, and lesions were confirmed after 7-8 days. After that, it was again placed under superhumid conditions for 24 hours to promote the second infection and to spread rice blast in the bat. About 3 to 4 days after the spread was promoted, a very small secondary lesion was observed, and the first drug spraying was performed.
上記以外の条件、例えば、供試薬液条件、散布方法、散布間隔、散布開始後の発病管理方法、病斑面積率の算出、および防除価の算出は、試験Ａと同様にして試験を行った。また、第２回の薬剤散布を行う場合も、その薬剤散布間隔は前記試験Ａと同様にした。 Conditions other than the above, for example, reagent solution conditions, spraying method, spraying interval, disease management method after spraying start, calculation of lesion area rate, and control value calculation were performed in the same manner as in Test A. . Moreover, also when performing the 2nd chemical | medical agent spraying, the chemical | medical agent spraying interval was made to be the same as that of the said test A. FIG.
なお試験は、下記表Ｂ１〜表Ｂ４の各表にある薬剤を１グループとして、各グループ毎に行った。 In addition, the test was conducted for each group, with the drugs in each table of Tables B1 to B4 below as one group.
結果は表Ｂ１〜表Ｂ４に示されるとおりであった。
Claims (16)
の化合物またはその酸付加塩と、
ストロビルリン系殺菌剤から選択される少なくとも１種の化合物と
を有効成分として含んでなる、殺菌性組成物。Following formula (1):
Or an acid addition salt thereof,
A bactericidal composition comprising at least one compound selected from strobilurin fungicides as an active ingredient.
の化合物またはその酸付加塩と、
ストロビルリン系殺菌剤から選択される少なくとも１種の化合物と
を含んでなる、殺菌用組み合わせ物。Following formula (1):
Or an acid addition salt thereof,
A sterilizing combination comprising at least one compound selected from strobilurin fungicides.
下記式（１）：
の化合物またはその酸付加塩と、
ストロビルリン系殺菌剤から選択される少なくとも１種の化合物と
を、同時にまたは別々に、処理すべき領域に適用することを含んでなる、方法。A method for controlling rice diseases,
Following formula (1):
Or an acid addition salt thereof,
Applying at least one compound selected from strobilurin fungicides to the area to be treated, simultaneously or separately.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002315503 | 2002-10-30 | ||
| JP2002315503 | 2002-10-30 | ||
| PCT/JP2003/013850 WO2004039156A1 (en) | 2002-10-30 | 2003-10-29 | Fungicidal compositions for the control of paddy rice diseases |
Publications (2)
| Publication Number | Publication Date |
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| JPWO2004039156A1 JPWO2004039156A1 (en) | 2006-02-23 |
| JP4558496B2 true JP4558496B2 (en) | 2010-10-06 |
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| JP2004548069A Expired - Fee Related JP4558496B2 (en) | 2002-10-30 | 2003-10-29 | Bactericidal composition for controlling rice plant diseases |
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|---|---|
| JP (1) | JP4558496B2 (en) |
| KR (1) | KR100764948B1 (en) |
| CN (1) | CN1327768C (en) |
| AR (1) | AR041728A1 (en) |
| AU (1) | AU2003280600A1 (en) |
| TW (1) | TWI320305B (en) |
| WO (1) | WO2004039156A1 (en) |
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| JP4880281B2 (en) * | 2005-10-21 | 2012-02-22 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Agricultural and horticultural bactericidal mixed composition |
| JP5132303B2 (en) * | 2007-12-26 | 2013-01-30 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Stabilized agrochemical solid pharmaceutical composition |
| CN102638984B (en) | 2009-12-09 | 2014-07-23 | 明治制果药业株式会社 | Stabilized composition for aqueous suspension agricultural chemical |
| JP5608508B2 (en) * | 2010-10-19 | 2014-10-15 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | Agricultural and horticultural fungicides |
| CN103271036B (en) * | 2012-05-31 | 2014-04-09 | 陕西上格之路生物科学有限公司 | Sterilization composition containing SYP-1620 |
| CN103214461B (en) * | 2013-04-22 | 2015-05-27 | 山东省联合农药工业有限公司 | Quinoline derivative and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| IL89029A (en) * | 1988-01-29 | 1993-01-31 | Lilly Co Eli | Fungicidal quinoline and cinnoline derivatives, compositions containing them, and fungicidal methods of using them |
| TW338038B (en) * | 1995-09-12 | 1998-08-11 | Basf Ag | Fungicidal quinolines |
| TW521072B (en) * | 1997-06-02 | 2003-02-21 | Meiji Seika Kaisha | 4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture |
| CN1193017C (en) * | 2000-05-30 | 2005-03-16 | 明治制果株式会社 | Rice blast control agents |
| JP2003055114A (en) * | 2001-08-14 | 2003-02-26 | Meiji Seika Kaisha Ltd | Fungicidal mix composition for paddy rice |
| TW200304772A (en) * | 2002-03-08 | 2003-10-16 | Meiji Seika Kaisha | Fungicidal composition for control of rice plant disease |
-
2003
- 2003-10-29 KR KR1020057007435A patent/KR100764948B1/en not_active IP Right Cessation
- 2003-10-29 CN CNB2003801024643A patent/CN1327768C/en not_active Expired - Fee Related
- 2003-10-29 WO PCT/JP2003/013850 patent/WO2004039156A1/en active Application Filing
- 2003-10-29 TW TW092130115A patent/TWI320305B/en not_active IP Right Cessation
- 2003-10-29 JP JP2004548069A patent/JP4558496B2/en not_active Expired - Fee Related
- 2003-10-29 AU AU2003280600A patent/AU2003280600A1/en not_active Abandoned
- 2003-10-30 AR ARP030103984A patent/AR041728A1/en unknown
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|---|---|
| TW200418384A (en) | 2004-10-01 |
| CN1708225A (en) | 2005-12-14 |
| KR20050059321A (en) | 2005-06-17 |
| AU2003280600A1 (en) | 2004-05-25 |
| CN1327768C (en) | 2007-07-25 |
| TWI320305B (en) | 2010-02-11 |
| WO2004039156A1 (en) | 2004-05-13 |
| AR041728A1 (en) | 2005-05-26 |
| JPWO2004039156A1 (en) | 2006-02-23 |
| KR100764948B1 (en) | 2007-10-08 |
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