JPS6145981B2 - - Google Patents
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- Publication number
- JPS6145981B2 JPS6145981B2 JP4977379A JP4977379A JPS6145981B2 JP S6145981 B2 JPS6145981 B2 JP S6145981B2 JP 4977379 A JP4977379 A JP 4977379A JP 4977379 A JP4977379 A JP 4977379A JP S6145981 B2 JPS6145981 B2 JP S6145981B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen atom
- present
- compound
- group
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000004009 herbicide Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 13
- 230000002363 herbicidal effect Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- -1 2-{4-(4-iodo-2-nitroanilino) Phenoxy}propionate ethyl ester Chemical compound 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002689 soil Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- 230000035784 germination Effects 0.000 description 6
- 230000012010 growth Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 4
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 4
- 235000005476 Digitaria cruciata Nutrition 0.000 description 4
- 235000006830 Digitaria didactyla Nutrition 0.000 description 4
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 4
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 4
- 244000025670 Eleusine indica Species 0.000 description 4
- 235000014716 Eleusine indica Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- 241000209763 Avena sativa Species 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 2
- 244000055702 Amaranthus viridis Species 0.000 description 2
- 235000004135 Amaranthus viridis Nutrition 0.000 description 2
- 235000007558 Avena sp Nutrition 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- 235000009344 Chenopodium album Nutrition 0.000 description 2
- 235000005484 Chenopodium berlandieri Nutrition 0.000 description 2
- 235000009332 Chenopodium rubrum Nutrition 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000006089 Phaseolus angularis Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 244000197975 Solidago virgaurea Species 0.000 description 2
- 235000000914 Solidago virgaurea Nutrition 0.000 description 2
- 240000007098 Vigna angularis Species 0.000 description 2
- 235000010711 Vigna angularis Nutrition 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LEWRZPGUAVNPFJ-UHFFFAOYSA-N (2-anilinophenyl) hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1NC1=CC=CC=C1 LEWRZPGUAVNPFJ-UHFFFAOYSA-N 0.000 description 1
- VJLYHTOSFSGXGH-CQSZACIVSA-N (2R)-1-[3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxybenzoyl]pyrrolidine-2-carboxylic acid Chemical group NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)N2[C@H](CCC2)C(=O)O)C=CC=1 VJLYHTOSFSGXGH-CQSZACIVSA-N 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005493 Chloridazon (aka pyrazone) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000001953 Hypotension Diseases 0.000 description 1
- 241000287127 Passeridae Species 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- WYKYKTKDBLFHCY-UHFFFAOYSA-N chloridazon Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1 WYKYKTKDBLFHCY-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 208000021822 hypotensive Diseases 0.000 description 1
- 230000001077 hypotensive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WJNRPILHGGKWCK-UHFFFAOYSA-N propazine Chemical compound CC(C)NC1=NC(Cl)=NC(NC(C)C)=N1 WJNRPILHGGKWCK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は新規な化合物及びその使用に関し、詳
しくは、一般式()
(式中、Xはハロゲン原子又はトリフルオロメチ
ル基を、R1は水素原子又は低級アルキル基を、
R2は水素原子、低級アルキル基、低級アルケニ
ル基又はベンジル基を示す。但し、R2が水素原
子のときは、Xはヨウ素原子又はフツ素原子を示
し、且つ、Xがトリフルオロメチル基のときは、
R1は水素原子を示す。)で表わされる化合物及び
該化合物類を有効成分として含有する選択的除草
剤に関するものである。
本発明の目的は該化合物類を工業的に有利に
得、簡便に使用出来しかも効果の確実な除草剤を
提供するにある。
本発明者らは種々のジフエニルアミン誘導体を
合成し、上記目的に適合するものを検討したとこ
ろ、前記一般式〔〕で表わされるアニリノフエ
ノキシカルボン酸誘導体が優れた選択的除草作用
を示すことを見い出し、更に生物学的及び物理化
学的研究を重ね、本発明を完成した。
本発明化合物はヒエ、メヒシバ、エンバク、ス
ズメノテツポウ等の禾本科雑草に対して極めて優
れた選択的除草作用を示し、しかも、イネ又はア
ズキ、大豆、ビート等の広葉作物には殆んど無害
であるという特性を有する。
本発明化合物は雑草に対し、発芽前、発芽後を
問わずどんな生育時期に処理しても優れた殺草効
力を示すが一般に同薬量使用した場合は発芽後処
理した場合の方がより高い活性が期待できる。
本発明化合物は茎葉散布処理で例えば禾本科雑
草のメヒシバを完全に枯殺する薬量でも大根、ア
ズキ、大豆、エンドウ、ホウレン草、ビート等の
広葉作物に対しては殆んど影響が見られずまた雑
草の発芽前土壌処理において、メヒシバの発芽を
完全に阻止する薬量でも広葉作物の種子には殆ん
ど影響が認められないなど、広葉作物に対する除
草剤による薬害の安全性が非常に高く、その適用
時期、適用場所、適用濃度等の適用範囲も極めて
大きい。また、本発明化合物は低濃度で使用でき
るので、人畜魚類に対する急性毒性等の心配が少
なく、安全に使用し得る。
また、本発明化合物は水田条件下においても畑
地条件下においても、イネに対しても選択性がみ
られ、ノビエを完全に枯殺する薬量でも、イネに
対しては影響が少ないという特性を有している。
また、本発明化合物は、きゆうりのべと病等の
植物病害に対する防除効果及び殺ダニ、殺虫効果
をも有する。
また、本発明化合物は、鎮痛作用、血圧降下作
用、抗炎症作用及び抗菌活性をも有しており、医
薬としても有用である。
本発明化合物は下記反応式により製造される。
但し、下記式中、Halはハロゲン原子を、R1′は低
級アルキル基を、R2′は低級アルキル基、低級ア
ルケニル基又はベンジル基を示す。
上記の反応は、酸結合剤の存在下、不活性溶媒
中において通常3〜6時間加熱還流して行われ
る。不活性溶媒としては、アセトン、メチルエチ
ルケトン、アセトニトリル、シクロルメタン等一
般の不活性溶媒が用いられ、酸結合剤としては炭
酸カリ、炭酸ナトリウム、ナトリウムメチラート
等が用いられる。上記式中、Halで表わされるハ
ロゲンとしては、通常、塩素又は臭素が使用され
る。
反応液を冷水に注いで適当な有機溶媒で抽出
し、有機溶媒層を水洗、乾燥後、溶媒を留去すれ
ば、エステル即ち、R1が低級アルキルである本
発明化合物が得られる。得られたエステルを常法
によりアルカリ加水分解すればR1が水素原子で
ある本発明化合物が得られる。
本発明化合物のうち、R2が水素原子である化
合物は、通常、上記反応式(1)により製造され、ま
た、R2が低級アルキル基、低級アルケニル基又
はベンジル基である化合物は、通常、上記反応式
(2)により製造される。
前記一般式〔〕で表わされる原料化合物は、
p−アミノフエノールと対応する置換ベンゼンと
を酸結合剤の存在下、極性溶媒中で反応させる
か、又はp−アニシジンと対応する置換ベンゼン
とを反応させた後還元することによつても得られ
る。p−アミノフエノールとベンゼンとの反応に
おいて用いられる酸結合剤としは、炭酸ソーダ、
カ性ソーダ等の無機塩基又はピリジン、トリメチ
ルアミン、トリブチルアミン、p−アミノフエノ
ール等の有機塩基が用いられるが有機塩基を用い
る方が好ましい。
次に実施例を挙げて本発明化合物の製造方法に
ついて更に詳しく説明する。
実施例 1
2−{4−(4−ヨード−2−ニトロアニリノ)
フエノキシ}プロピオン酸エチルエステル(化
合物番号1)
4−(4−ヨード−2−ニトロアニリノ)フエ
ノール4.3gと2−ブロモプロピオン酸エチル2.4
gをメチルエチルケトン50mlに溶解し、無水炭酸
カリウム2gを加え撹拌下に5時間加熱還流し
た。その後反応液を水に注ぎ、酢酸エチルで抽出
し水洗後、無水硫酸マグネシウムで乾燥し、溶媒
を留去して目的物5gを得た。m.p.70〜71℃
実施例 2
−{4−(N−エチル−4−クロロ−2−ニトロ
アニリノ)フエノキシ}プロピオン酸エチルエ
ステル(化合物番号3)
N・N−ジメチルホルムアミド50ml中に50%水
素化ナトリウム0.5gを懸濁し、冷却下、2−{4
−(4−クロロ−2−ニトロアニリノ)フエノキ
シ}プロピオン酸エチルエステル3gを少量ずつ
加え、そのまま30分撹拌した後、ヨウ化エチル
1.9gを加え徐々に加温して50℃で5時間反応さ
せた。その後反応液を水にあけ、酢酸エチルで抽
出し水洗後、無水硫酸マグネシウムで乾燥し、溶
媒を留去して赤黒色油状の粗製物3gを得た。
該粗製物をシリカゲルカラムクロマト(展開溶
媒、ヘキサン:酢酸エチル=4:1)で精製し目
的物の結晶2.5gを得た。m.p.62〜65℃
第1表に本発明の代表化合物を示す。
The present invention relates to a novel compound and its use, and in particular, the present invention relates to a novel compound and its use, and in particular, the general formula () (In the formula, X is a halogen atom or a trifluoromethyl group, R 1 is a hydrogen atom or a lower alkyl group,
R 2 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a benzyl group. However, when R 2 is a hydrogen atom, X represents an iodine atom or a fluorine atom, and when X is a trifluoromethyl group,
R 1 represents a hydrogen atom. ) and selective herbicides containing the compounds as active ingredients. The object of the present invention is to provide a herbicide that can be industrially advantageously obtained, is easy to use, and is highly effective. The present inventors synthesized various diphenylamine derivatives and examined those suitable for the above purpose, and found that the anilinophenoxycarboxylic acid derivative represented by the general formula [] exhibits excellent selective herbicidal action. After making this discovery and conducting further biological and physicochemical research, the present invention was completed. The compound of the present invention exhibits extremely excellent selective herbicidal activity against weeds of the grass family such as barnyard grass, crabgrass, oat, and sparrow gnome, and is almost harmless to rice or broad-leaved crops such as adzuki beans, soybeans, and beets. It has the following characteristics. The compound of the present invention exhibits excellent herbicidal efficacy against weeds when treated at any growth period, whether before or after germination, but in general, when the same dosage is used, the efficacy is higher when treated after germination. You can expect it to be active. The compound of the present invention has almost no effect on broad-leaved crops such as radish, adzuki beans, soybeans, peas, spinach, beets, etc., even at doses that completely kill the grasshopper, a common weed, when applied to leaves. In addition, in pre-emergence soil treatment for weeds, even at doses that completely inhibit the germination of crabgrass, there is almost no effect on the seeds of broad-leaved crops, indicating that herbicides are extremely safe against chemical damage to broad-leaved crops. The range of application, such as application period, application location, and application concentration, is also extremely wide. In addition, since the compound of the present invention can be used at low concentrations, there is little concern about acute toxicity to livestock and fish, and it can be used safely. In addition, the compound of the present invention is selective for rice both under paddy field conditions and upland conditions, and has the property that even a dose that completely kills noviidae has little effect on rice. have. The compound of the present invention also has a controlling effect on plant diseases such as downy mildew of Japanese cucumber, and also has acaricidal and insecticidal effects. The compounds of the present invention also have analgesic, hypotensive, anti-inflammatory, and antibacterial activities, and are useful as medicines. The compound of the present invention is produced by the following reaction formula.
However, in the following formula, Hal represents a halogen atom, R 1 ' represents a lower alkyl group, and R 2 ' represents a lower alkyl group, a lower alkenyl group, or a benzyl group. The above reaction is usually carried out under heating under reflux for 3 to 6 hours in an inert solvent in the presence of an acid binder. As the inert solvent, common inert solvents such as acetone, methyl ethyl ketone, acetonitrile, and cyclomethane are used, and as the acid binder, potassium carbonate, sodium carbonate, sodium methylate, etc. are used. In the above formula, chlorine or bromine is usually used as the halogen represented by Hal. The reaction solution is poured into cold water, extracted with a suitable organic solvent, the organic solvent layer is washed with water, dried, and the solvent is distilled off to obtain an ester, that is, a compound of the present invention in which R 1 is lower alkyl. The compound of the present invention in which R 1 is a hydrogen atom can be obtained by subjecting the obtained ester to alkaline hydrolysis using a conventional method. Among the compounds of the present invention, compounds in which R 2 is a hydrogen atom are usually produced by the above reaction formula (1), and compounds in which R 2 is a lower alkyl group, a lower alkenyl group, or a benzyl group are usually produced by The above reaction formula
Manufactured by (2). The raw material compound represented by the general formula [] is
It can also be obtained by reacting p-aminophenol with the corresponding substituted benzene in the presence of an acid binder in a polar solvent, or by reacting p-anisidine with the corresponding substituted benzene followed by reduction. . Acid binders used in the reaction between p-aminophenol and benzene include soda carbonate,
Inorganic bases such as caustic soda or organic bases such as pyridine, trimethylamine, tributylamine, p-aminophenol are used, but it is preferable to use organic bases. Next, the method for producing the compound of the present invention will be explained in more detail with reference to Examples. Example 1 2-{4-(4-iodo-2-nitroanilino)
Phenoxy}propionate ethyl ester (compound number 1) 4-(4-iodo-2-nitroanilino)phenol 4.3g and ethyl 2-bromopropionate 2.4g
g was dissolved in 50 ml of methyl ethyl ketone, 2 g of anhydrous potassium carbonate was added, and the mixture was heated under reflux for 5 hours with stirring. Thereafter, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 5 g of the target product. mp70-71℃ Example 2 -{4-(N-Ethyl-4-chloro-2-nitroanilino)phenoxy}propionic acid ethyl ester (Compound No. 3) 50% sodium hydride 0.5 in 50 ml of N·N-dimethylformamide g was suspended, and under cooling, 2-{4
-(4-Chloro-2-nitroanilino)phenoxy}propionic acid ethyl ester (3 g) was added little by little, and after stirring for 30 minutes, ethyl iodide was added.
1.9 g was added and the mixture was gradually heated to react at 50° C. for 5 hours. Thereafter, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 3 g of a red-black oily crude product. The crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate = 4:1) to obtain 2.5 g of crystals of the desired product. mp62-65°C Table 1 shows representative compounds of the present invention.
【表】【table】
【表】
本発明除草剤は前記一般式()で示される化
合物の1又は2以上の適当量を担体と混合し、濃
薬の通常の使用形態、例えば、水和剤、乳剤、粒
剤等の形で使用される。固体担体としてはタル
ク、ベントナイト、クレー、ケイソウ土等が挙げ
られ、液体担体としては水、アルコール、ベンゼ
ン、キシレン、ケロシン、鉱油、シクロヘキサ
ン、シクロヘキサノン、ジメチルホルムアミド等
が使用される。これらの製剤において均一な、か
つ安定な形態をとるために必要ならば界面活性剤
を添加することもできる。
製剤にあたつては、通常の農薬の製剤方法に準
ずるものであり、例えば水和剤は有効成分及び固
体担体の適当量及び必要ならば界面活性剤を添加
して均一に混合し、微細に粉砕することにより得
られる。水和剤中の有効成分含量は約5〜80%、
好ましくは10〜60%が適当である。
乳剤は適当量の有効成分を界面活性剤を加え、
又は加えずして前述した液体の担体に十分溶解さ
せることにより得られ、有効成分含量は約5〜70
%、特に20〜60%が好ましい。粒剤においては適
当量の有効成分及び固体の担体を、必要ならば界
面活性剤と共に、均一に混合し、微細に粉砕し、
さらに造粒機にて直径0.5〜1.5mm、好ましくは0.5
〜1.0mmの粒状物にする方法が行われる。粒剤中
における有効成分量は約0.5〜30%であり、特に
1〜10%が望ましい。
この様にして得られた水和剤、乳剤は水で所定
の濃度に希釈して懸濁液あるいは乳濁液として、
粒剤はそのまま、雑草の発芽前に土壌表面処理若
しくは土壌混和処理、あるいは雑草の発芽後に茎
葉散布処理される。実際に本発明除草剤を適用す
るにあたつては10アール当り有効成分10g以上、
好ましくは25g以上の適当量が施用される。
また本発明除草剤は公知の殺菌剤、殺虫剤、殺
ダニ剤、除草剤、植物生長調整剤等と混合して使
用することもできる。特に除草剤と混合使用する
ことにより使用薬量を減少させ、また省力化をも
たらすのみならず、両薬剤の相乗作用による一層
高い効果も期待できる。本発明除草剤と混合使用
するにふさわしい公知の除草剤としてはシマジン
剤、プロパジン剤、プロメトリン剤等のトリアジ
ン系除草剤、ベタナール剤等のカーバメート系除
草剤、リニユロン剤、トリブニル剤等の尿素系除
草剤、2・4−PA剤等のフエノキシアルカンカ
ルボン酸系除草剤、ピラゾン剤、レナシル剤等の
複素環系除草剤等が挙げられる。
次に本発明除草剤に関する実施例を若干示す
が、有効成分化合物、添加物及び添加割合は本実
施例にのみ限定されることなく広い範囲で変更可
能である。
実施例 3
乳 剤
化合物1 25部
ジメチルホルムアミド 47部
キシレン 20部
ポリオキシエチレンフエニルエーテル 8部
以上を混合溶解して有効成分25%の乳剤を得
た。
実施例 4
水和剤
化合物3 30部
珪藻土 56部
高級アルコール硫酸エステル 8部
ホワイトカーボン 6部
以上を均一に混合し、微細に粉砕して有効成分
30%の水和剤を得た。
実施例 5
粒 剤
化合物6 3部
ベントナイト 8部
タルク 85部
ポリオキシエチレンアルキルアリールサルフエイ
ト 4部
以上を均一に混合粉砕し、造粒機にて径0.5〜
1.0mmに造粒して有効成分3%の粒剤を得た。
次に試験例を示して本発明除草剤の有効性を証
明する。
試験例 1
土壌処理試験
250cm2ポツトに土壌を詰め、メヒシバ、エンバ
ク、アカザ、イヌビエ、春菊、大豆の種子を播
き、各種子が見えない程度に覆土した。各供試化
合物の乳剤を水で希釈して調整した所定濃度の薬
液を100/10aの割合で土壌表面に散布処理し
た。3週間後に各雑草の生育状況を調査した。無
処理と同等の生育程度を0、枯死又は不発芽を10
とする0〜10の11段階で生育状況を表わし第2表
に示す結果を得た。[Table] The herbicide of the present invention can be prepared by mixing an appropriate amount of one or more of the compounds represented by the above general formula () with a carrier, and using the usual forms of concentrated medicine, such as wettable powders, emulsions, granules, etc. used in the form of Examples of solid carriers include talc, bentonite, clay, diatomaceous earth, etc., and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide, and the like. If necessary, a surfactant may be added in order to obtain a uniform and stable form in these preparations. The formulation method is similar to the usual formulation method for agricultural chemicals.For example, for wettable powders, the active ingredient and solid carrier are added in appropriate amounts and a surfactant if necessary, mixed uniformly, and finely dispersed. Obtained by grinding. The active ingredient content in the hydrating agent is approximately 5-80%,
Preferably, 10 to 60% is appropriate. Emulsions are made by adding appropriate amounts of active ingredients and surfactants.
Alternatively, it can be obtained by sufficiently dissolving it in the liquid carrier mentioned above without adding it, and the active ingredient content is about 5 to 70%.
%, especially 20-60% is preferred. For granules, appropriate amounts of the active ingredient and solid carrier are uniformly mixed together with a surfactant, if necessary, and finely ground.
Furthermore, in a granulator, the diameter is 0.5 to 1.5 mm, preferably 0.5 mm.
A method of making granules of ~1.0 mm is performed. The amount of active ingredient in the granules is approximately 0.5 to 30%, preferably 1 to 10%. The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion.
The granules can be treated as they are by soil surface treatment or soil mixing treatment before weed germination, or by spraying on foliage after weed germination. When actually applying the herbicide of the present invention, 10 g or more of the active ingredient per 10 ares,
Preferably, an appropriate amount of 25 g or more is applied. The herbicide of the present invention can also be used in combination with known bactericides, insecticides, acaricides, herbicides, plant growth regulators, and the like. In particular, when used in combination with a herbicide, not only the amount of chemicals used can be reduced and labor savings can be achieved, but even higher effects can be expected due to the synergistic action of both chemicals. Known herbicides suitable for use in combination with the herbicide of the present invention include triazine herbicides such as simazine, propazine, and promethrin, carbamate herbicides such as betanal, and urea herbicides such as linyuron and tribunyl. Examples include phenoxyalkane carboxylic acid herbicides such as 2,4-PA agents, and heterocyclic herbicides such as pyrazone agents and renacil agents. Next, some examples regarding the herbicide of the present invention will be shown, but the active ingredient compounds, additives, and addition ratios are not limited to these examples and can be varied within a wide range. Example 3 Emulsion Compound 1 25 parts Dimethylformamide 47 parts Xylene 20 parts Polyoxyethylene phenyl ether 8 parts The above ingredients were mixed and dissolved to obtain an emulsion containing 25% of the active ingredient. Example 4 Wettable powder compound 3 30 parts diatomaceous earth 56 parts Higher alcohol sulfate ester 8 parts White carbon 6 parts The above are mixed uniformly and finely ground to form the active ingredients.
A 30% hydrating powder was obtained. Example 5 Granule Compound 6 3 parts bentonite 8 parts talc 85 parts polyoxyethylene alkylaryl sulfate 4 parts The above was mixed and ground uniformly, and the diameter was 0.5 to 0.5 in a granulator.
It was granulated to a size of 1.0 mm to obtain granules containing 3% of the active ingredient. Next, test examples will be shown to demonstrate the effectiveness of the herbicide of the present invention. Test Example 1 Soil treatment test Two 250cm pots were filled with soil, and seeds of crabgrass, oat, pigweed, goldenrod, chrysanthemum, and soybean were sown, and the soil was covered to the extent that each seed was not visible. A chemical solution with a predetermined concentration prepared by diluting an emulsion of each test compound with water was sprayed onto the soil surface at a ratio of 100/10a. Three weeks later, the growth status of each weed was investigated. 0 indicates the same level of growth as no treatment, 10 indicates withering or non-germination.
The growth status was expressed in 11 stages from 0 to 10, and the results shown in Table 2 were obtained.
【表】【table】
【表】
試験例 2
茎葉処理試験
200cm2ポツトに土壌を詰め、メヒシバ、エンバ
ク、アカザ、イヌビエ、の種子を播いて軽く覆土
して温室内で生育させた。雑草が2〜4葉期に生
育したとき、各供試化合物の乳剤を水て希釈して
調整した所定濃度の薬液を100/10aの割合で茎
葉散布処理した。3週間後に各雑草の生育状況を
調整し、試験例1と同様の判定基準に従つて生育
状況を表わし、第3表に示す結果を得た。[Table] Test Example 2 Stem and Leaf Treatment Test Two 200 cm pots were filled with soil, and seeds of crabgrass, oat, pigweed, and goldenrod were sown, lightly covered with soil, and grown in a greenhouse. When the weeds grew to the 2-4 leaf stage, a chemical solution of a predetermined concentration prepared by diluting an emulsion of each test compound with water was sprayed on the leaves at a ratio of 100/10a. After three weeks, the growth status of each weed was adjusted and expressed according to the same criteria as Test Example 1, and the results shown in Table 3 were obtained.
【表】【table】
Claims (1)
ル基を、R1は水素原子又は低級アルキル基を、
R2は水素原子、低級アルキル基、低級アルケニ
ル基又はベンジル基を示す。但し、R2が水素原
子のときは、Xはヨウ素原子又はフツ素原子を示
し、且つ、Xがトリフルオロメチル基のときは、
R1は水素原子を示す。) で表わされる化合物。 2 一般式 (式中、Xはハロゲン原子又はトリフルオロメチ
ル基を、R1は水素原子又は低級アルキル基を、
R2は水素原子、低級アルキル基、低級アルケニ
ル基又はベンジル基を示す。但し、R2が水素原
子のときは、Xはヨウ素原子又はフツ素原子を示
し、且つ、Xがトリフルオロメチル基のときは、
R1は水素原子を示す。) で表わされる化合物を有効成分とする除草剤。[Claims] 1. General formula (In the formula, X is a halogen atom or a trifluoromethyl group, R 1 is a hydrogen atom or a lower alkyl group,
R 2 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a benzyl group. However, when R 2 is a hydrogen atom, X represents an iodine atom or a fluorine atom, and when X is a trifluoromethyl group,
R 1 represents a hydrogen atom. ) A compound represented by 2 General formula (In the formula, X is a halogen atom or a trifluoromethyl group, R 1 is a hydrogen atom or a lower alkyl group,
R 2 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a benzyl group. However, when R 2 is a hydrogen atom, X represents an iodine atom or a fluorine atom, and when X is a trifluoromethyl group,
R 1 represents a hydrogen atom. ) A herbicide containing the compound represented by as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4977379A JPS55141449A (en) | 1979-04-24 | 1979-04-24 | Diphenylamine derivative and selective herbicide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4977379A JPS55141449A (en) | 1979-04-24 | 1979-04-24 | Diphenylamine derivative and selective herbicide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS55141449A JPS55141449A (en) | 1980-11-05 |
JPS6145981B2 true JPS6145981B2 (en) | 1986-10-11 |
Family
ID=12840480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4977379A Granted JPS55141449A (en) | 1979-04-24 | 1979-04-24 | Diphenylamine derivative and selective herbicide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS55141449A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0517105Y2 (en) * | 1986-09-25 | 1993-05-07 |
-
1979
- 1979-04-24 JP JP4977379A patent/JPS55141449A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0517105Y2 (en) * | 1986-09-25 | 1993-05-07 |
Also Published As
Publication number | Publication date |
---|---|
JPS55141449A (en) | 1980-11-05 |
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