JPS6113441B2 - - Google Patents
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- Publication number
- JPS6113441B2 JPS6113441B2 JP8609877A JP8609877A JPS6113441B2 JP S6113441 B2 JPS6113441 B2 JP S6113441B2 JP 8609877 A JP8609877 A JP 8609877A JP 8609877 A JP8609877 A JP 8609877A JP S6113441 B2 JPS6113441 B2 JP S6113441B2
- Authority
- JP
- Japan
- Prior art keywords
- present
- compounds
- rate
- compound
- diphosphonic acid
- 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
Links
- 230000002363 herbicidal effect Effects 0.000 claims description 25
- 239000004009 herbicide Substances 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- OEAFYMDEEMRBOS-UHFFFAOYSA-N [phosphono-(pyridin-2-ylamino)methyl]phosphonic acid Chemical class OP(O)(=O)C(P(O)(O)=O)NC1=CC=CC=N1 OEAFYMDEEMRBOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 28
- 239000000203 mixture Substances 0.000 description 17
- 244000025254 Cannabis sativa Species 0.000 description 13
- 238000009472 formulation Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 240000007594 Oryza sativa Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- RHVWSRKGJFLDFG-UHFFFAOYSA-N [aminooxy(hydroxy)phosphoryl]methylphosphonic acid Chemical compound NOP(O)(=O)CP(O)(O)=O RHVWSRKGJFLDFG-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000006385 2-(3-methylpyridyl) group Chemical group [H]C1=C([H])C([H])=C(C(*)=N1)C([H])([H])[H] 0.000 description 4
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 4
- 240000008067 Cucumis sativus Species 0.000 description 4
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 4
- 240000003768 Solanum lycopersicum Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000000887 hydrating effect Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 235000009849 Cucumis sativus Nutrition 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000269837 Artemisia dubia Species 0.000 description 2
- 240000006891 Artemisia vulgaris Species 0.000 description 2
- 241000234653 Cyperus Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 2
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 2
- 235000005476 Digitaria cruciata Nutrition 0.000 description 2
- 235000006830 Digitaria didactyla Nutrition 0.000 description 2
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 2
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 2
- 241001517923 Douglasiidae Species 0.000 description 2
- 244000025670 Eleusine indica Species 0.000 description 2
- 235000014716 Eleusine indica Nutrition 0.000 description 2
- 244000184734 Pyrus japonica Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- RGDQRXPEZUNWHX-UHFFFAOYSA-N 3-methylpyridin-2-amine Chemical compound CC1=CC=CN=C1N RGDQRXPEZUNWHX-UHFFFAOYSA-N 0.000 description 1
- MAXBVGJEFDMHNV-UHFFFAOYSA-N 5-chloropyridin-2-amine Chemical compound NC1=CC=C(Cl)C=N1 MAXBVGJEFDMHNV-UHFFFAOYSA-N 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001076438 Oxya japonica Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 244000134552 Plantago ovata Species 0.000 description 1
- 235000003421 Plantago ovata Nutrition 0.000 description 1
- 244000234609 Portulaca oleracea Species 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 239000009223 Psyllium Substances 0.000 description 1
- 240000001341 Reynoutria japonica Species 0.000 description 1
- 235000018167 Reynoutria japonica Nutrition 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- 241000251778 Squalus acanthias Species 0.000 description 1
- HBGRETPFBONMPF-UHFFFAOYSA-N [phosphono-(pyridin-4-ylamino)methyl]phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)NC1=CC=NC=C1 HBGRETPFBONMPF-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical class OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLZLEPNAKIFDQJ-UHFFFAOYSA-N n-pyridin-2-ylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=N1 VLZLEPNAKIFDQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229940070687 psyllium Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Description
本発明は、一般式
〔式中、R1、R2、R3は、水素原子または低級アル
キル基を示し、Ｘは、水素原子、低級アルキル
基、ハロゲン原子またはアミノ基を示し、ｎは、
１または２を示す。〕
で示されるＮ−ピリジル−アミノメチレンジホス
ホン酸系化合物（以下、単に本発明化合物とい
う。）の１種または２種以上を有効成分として含
有してなる除草剤に関するものである。
本発明化合物の中で、Ｎ−（４−ピリジル）ア
ミノメチレンジホスホン酸は、ツアイトシユリフ
ト・ヒユア・アンオルガニツシエ・ウント・アル
ゲマイネ・ヒエミー（Zeitschrift fu¨r
anorganische und allgemeine chemie）第389巻
119頁（1972年）に記載されているが、該化合物
の除草活性の有無については、全く記載されてい
ない。
本発明化合物は、上記化合物１種を除いては、
すべて文献未記載の新規化合物である。
従来、農園芸用除草剤として、各種の除草剤が
開発され、市販されているが、莖葉処理型除草剤
においては、充分満足なものが見い出されていな
い。例えば、莖葉処理型除草剤として、１・1′−
ジメチル−４・4′−ビピリジニウムジクロライド
を有効成分とする除草剤（一般名：パラコート）
が知られているが、この除草剤は、散布除草後の
再生が迅速、すなわち薬効の持続効果が低く、且
つ、毒性も高いという欠点も有している。
また、従来の除草剤では、各種の多年生雑草を
広範囲に殺草することは、極めて困難であつた。
本発明者等はジホスホン酸系化合物について、農
薬的な生理活性の有無について種々研究した結
果、本発明化合物が優れた除草活性を有すること
を見い出したものである。
本発明化合物は、植物の発芽前処理（土壤処
理）においては、全く殺草効力がないにもかかわ
らず植物の発芽後処理（莖葉処理）により極めて
強い除草効力を有し、特に従来除草困難であつた
チガヤ、ジヨンソングラス、キシユウスズメノヒ
エ、ヨモギ、ハマスゲ、ギシギシ等の多年生雑草
を広範囲に、殺草し得るものである。
一方、本発明化合物は、莖葉処理において、綿
に対しては、殺草効力がほとんどなく、すなわち
綿に対する薬害がほとんどないという特色も有し
ている。
また、本発明は、本発明化合物のアルカリ金属
塩、アルカリ土類塩、アンモニウム塩、および有
機アミン塩も包含するものであり、これらの塩も
本発明化合物と同様に優れた殺草効力を有するも
のである。
本発明化合物は次式に示す方法により容易に合
成することができる。
〔式中、R1、R2、R3、Ｘおよびｎは前記と同じ。
Ｙは低級アルキル基を示す。〕
上式の化学反応式（）および（）の反応
は、同時に進行させるものである。すなわち、ア
ミノピリジン誘導体、オルトカルボン酸エステル
およびジアルキルホスフアイトの３種の出発物質
を同時に混合し、この混合物を加熱撹拌すること
によりジホスホン酸のエステルが生成し、更に、
このエステルを塩酸等の酸で加水分解することに
より容易に目的物が得られる。
但し、Ｘがアミノ基の場合には、アセチル化し
て、アミノ基の窒素原子を保護して反応せしめる
か若しくはニトロアミノピリジンを反応せしめた
後還元することにより目的物が得られる。次に本
発明化合物の合成例を具体的に挙げて説明する。
但し、この合成例のみに限定されるものではな
い。
合成例 １
Ｎ−〔２−（３−メチルピリジル）〕アミノメチ
レンジホスホン酸の合成
２−アミノ−３−メチルピリジン54.0ｇ（0.5
モル）、オルトギ酸エチル85.1ｇ（0.575モル）お
よびジエチルホスフアイト138ｇ（1.0モル）混合
加温し生成するエチルアルコールを留去しながら
油浴で150℃で１時間加熱する。
反応終了後低沸留去（130℃／20mmHg）を行な
うことにより、Ｎ−〔２−（３−メチルピリジ
ル）〕アミノメチレンジホスホン酸テトラエチル
エステル198.5ｇが得られる。この一部を採取
し、薄層クロマトグラフイー（担体：シリカゲ
ル、展開溶媒：ヘキサン−アセトン１：１）で精
製することにより屈折率Ｎ２０ Ｄ＝1.4990の純品が得
られる。
次に、上記生成物を室温下で濃塩酸100mlを少
量ずつ添加して後、１時間加熱還流することによ
り、Ｎ−〔２−（３−メチルピリジル）〕アミノメ
チレンジホスホン酸の結晶を得る。
濾過水洗、エタノール洗滌して、乾燥後の得量
は、124.6ｇ（収率88.4％）である。
濃塩酸で再結晶して、Ｎ−〔２−（３−メチルピ
リジル）〕アミノメチレンジホスホン酸（分解点
297〜298℃）の純品が得られる。
この元素分析値は、C7H12N2O6P2として、分析
値と計算値は、次のとおりである。
Ｃ Ｈ Ｎ
分析値 26.66％ 3.53％ 10.34％
計算値 26.86％ 3.73％ 10.44％
合成例 ２
Ｎ−〔２−（５−クロルピリジル）〕アミノメチ
レンジホスホン酸の合成
２−アミノ−５−クロルピリジン5.1ｇ（0.04
モル）、オルトギ酸エチル7.4ｇ（0.05モル）およ
びジエチルホスフアイト11ｇ（0.08モル）を混合
加温し、生成するエチルアルコールを留去しなが
ら、油浴で150℃で２時間加熱する。反応終了
後、反応混合物を室温で放置し、析出してくるＮ
−〔２−（５−クロルピリジル）〕アミノメチレン
ジホスホン酸テトラエチルエステルの結晶を濾別
した。
収量は11.3ｇ（収率68％）である。該結晶をエ
ーテルで再結晶すると融点103〜104℃の純品が得
られる。
次に、上記の結晶５ｇに濃塩酸３mlを添加し、
湯浴上で３時間加熱して、Ｎ−〔２−（５−クロル
ピリジル）〕アミノメチレンジホスホン酸の白色
結晶が得られる。濾別し、水、エタノールで洗浄
して純品を得る。収量3.3ｇ（収率92％）で、融
点285〜287℃（但し、287℃で分解）である。こ
の元素分析値はC5H9N2O5P2Clとして、分析値と
計算値は次のとおりである。
Ｃ Ｈ Ｎ
分析値 23.61％ 2.76％ 8.91％
計算値 23.82％ 3.00％ 9.26％
次に、合成例１、合成例２等に準じて合成した
本発明化合物を第１表に示す。但し、本発明化合
物は、これらのみに限定されるものではない。
尚、これらの化合物の番号は以下の配合例、試験
例において参照される。
The present invention is based on the general formula [In the formula, R 1 , R 2 and R 3 represent a hydrogen atom or a lower alkyl group, X represents a hydrogen atom, a lower alkyl group, a halogen atom or an amino group, and n is
Indicates 1 or 2. ] The present invention relates to a herbicide containing one or more of the following N-pyridyl-aminomethylene diphosphonic acid compounds (hereinafter simply referred to as compounds of the present invention) as an active ingredient. Among the compounds of the present invention, N-(4-pyridyl)aminomethylene diphosphonic acid is a compound of the present invention.
anorganische und allgemeine chemie) Volume 389
119 (1972), but there is no mention of whether or not the compound has herbicidal activity. The compounds of the present invention, except for one of the above compounds, include:
All of these are new compounds that have not been described in any literature. Conventionally, various herbicides have been developed and commercially available as agricultural and horticultural herbicides, but no fully satisfactory herbicide has been found as a foliar treatment type herbicide. For example, as a foliar treatment herbicide, 1・1'-
Herbicide containing dimethyl-4,4'-bipyridinium dichloride as an active ingredient (generic name: paraquat)
However, this herbicide has the disadvantage that it regenerates rapidly after spraying, that is, its medicinal effect is low in duration, and it is also highly toxic. Furthermore, it has been extremely difficult to kill various perennial weeds over a wide range with conventional herbicides.
The present inventors conducted various studies on the presence or absence of agricultural physiological activity of diphosphonic acid compounds, and as a result, they discovered that the compounds of the present invention have excellent herbicidal activity. Although the compound of the present invention has no herbicidal effect at all in the pre-emergence treatment of plants (soil treatment), it has an extremely strong herbicidal effect in the post-emergence treatment (leaf treatment) of plants, and it is particularly difficult to weed with conventional methods. It is capable of killing a wide range of perennial weeds such as perennial weeds, Japanese grass, Japanese grasshopper, mugwort, Japanese commonweed, and snail grass. On the other hand, the compound of the present invention also has the characteristic that it has almost no herbicidal effect on cotton in the treatment of leaves, that is, it causes almost no phytotoxicity to cotton. The present invention also includes alkali metal salts, alkaline earth salts, ammonium salts, and organic amine salts of the compounds of the present invention, and these salts also have excellent herbicidal efficacy similar to the compounds of the present invention. It is something. The compound of the present invention can be easily synthesized by the method shown in the following formula. [In the formula, R 1 , R 2 , R 3 , X and n are the same as above.
Y represents a lower alkyl group. ] The reactions in the above chemical reaction formulas () and () are allowed to proceed simultaneously. That is, by simultaneously mixing three starting materials, an aminopyridine derivative, an orthocarboxylic acid ester, and a dialkyl phosphite, and heating and stirring this mixture, a diphosphonic acid ester is produced, and further,
The desired product can be easily obtained by hydrolyzing this ester with an acid such as hydrochloric acid. However, when X is an amino group, the desired product can be obtained by acetylating and reacting while protecting the nitrogen atom of the amino group, or by reacting with nitroaminopyridine and then reducing. Next, specific examples of synthesis of the compounds of the present invention will be explained. However, it is not limited to this synthesis example. Synthesis Example 1 Synthesis of N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid 2-Amino-3-methylpyridine 54.0g (0.5
85.1 g (0.575 mol) of ethyl orthoformate and 138 g (1.0 mol) of diethyl phosphite were mixed and heated, and heated in an oil bath at 150° C. for 1 hour while distilling off the ethyl alcohol produced. After completion of the reaction, 198.5 g of N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid tetraethyl ester is obtained by performing low boiling distillation (130° C./20 mmHg). A portion of this is collected and purified by thin layer chromatography (carrier: silica gel, developing solvent: hexane-acetone 1:1) to obtain a pure product with a refractive index of N 20 D =1.4990. Next, 100 ml of concentrated hydrochloric acid is added little by little to the above product at room temperature, and the mixture is heated under reflux for 1 hour to obtain crystals of N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid. . The amount obtained after filtering, washing with water, washing with ethanol, and drying was 124.6 g (yield: 88.4%). Recrystallize from concentrated hydrochloric acid to obtain N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid (decomposition point
297-298℃) is obtained. The elemental analysis value is C 7 H 12 N 2 O 6 P 2 , and the analysis value and calculated value are as follows. C H N Analytical value 26.66% 3.53% 10.34% Calculated value 26.86% 3.73% 10.44% Synthesis example 2 Synthesis of N-[2-(5-chloropyridyl)]aminomethylene diphosphonic acid 2-Amino-5-chloropyridine 5.1g (0.04
7.4 g (0.05 mol) of ethyl orthoformate and 11 g (0.08 mol) of diethyl phosphite are mixed and heated, and heated in an oil bath at 150° C. for 2 hours while distilling off the ethyl alcohol produced. After the reaction is complete, the reaction mixture is left at room temperature to remove the precipitated N.
-[2-(5-Chlorpyridyl)]aminomethylene diphosphonic acid tetraethyl ester crystals were separated by filtration. The yield was 11.3g (yield 68%). When the crystals are recrystallized with ether, a pure product with a melting point of 103-104°C is obtained. Next, add 3 ml of concentrated hydrochloric acid to 5 g of the above crystals,
After heating on a water bath for 3 hours, white crystals of N-[2-(5-chloropyridyl)]aminomethylene diphosphonic acid are obtained. Filter and wash with water and ethanol to obtain a pure product. The yield was 3.3 g (yield 92%), and the melting point was 285-287°C (decomposed at 287°C). The elemental analysis value is C 5 H 9 N 2 O 5 P 2 Cl, and the analysis value and calculated value are as follows. C H N Analytical value 23.61% 2.76% 8.91% Calculated value 23.82% 3.00% 9.26% Next, the compounds of the present invention synthesized according to Synthesis Example 1, Synthesis Example 2, etc. are shown in Table 1. However, the compounds of the present invention are not limited to these.
The numbers of these compounds are referred to in the following formulation examples and test examples.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
以下の試験例４において対照薬剤とし
て用いた。
本発明化合物を有効成分とする除草剤を実際に
使用する際には、該化合物の１種または２種以上
を公知の処方にしたがつて、不活性な適当な担体
と組合わせ、水和剤、フロアブル、粉剤、粒剤若
しくは、アルカリ金属塩、アルカリ土類塩、アン
モニウム塩、有機アミン塩等の水溶液剤または固
型水溶剤などの使い易い適宜の形態に調製するの
が適当である。この場合用いられる担体は、固体
担体としては、例えばクレー、タルク、ベントナ
イト、ケイソウ土などが挙げられる。また液体担
体としては、例えば水、アルコール類、アセト
ン、ジメチルホルムアマイドなどが挙げられる。
また製剤上の補助剤として、乳化剤、分散剤、
浸透剤などの界面活性剤を適宜使用し得る。次に
本発明化合物を有効成分とする除草剤の配合例を
具体的に挙げて説明する。但し、これら配合例の
みに限定されるものではない。尚、以下の「部」
は、重量部を意味するものである。
配合例 １
水和剤[Table] Used as a control drug in Test Example 4 below.
When actually using a herbicide containing a compound of the present invention as an active ingredient, one or more of the compounds are combined with a suitable inert carrier according to a known formulation, and a hydrating powder is added. , flowables, powders, granules, aqueous solutions or solid aqueous solutions of alkali metal salts, alkaline earth salts, ammonium salts, organic amine salts, etc., which are suitable for easy use. Examples of solid carriers used in this case include clay, talc, bentonite, and diatomaceous earth. Examples of liquid carriers include water, alcohols, acetone, and dimethylformamide. In addition, as formulation aids, emulsifiers, dispersants,
Surfactants such as penetrants may be used as appropriate. Next, specific formulation examples of herbicides containing the compound of the present invention as an active ingredient will be explained. However, the composition is not limited to these formulation examples. In addition, the following “departments”
means parts by weight. Formulation example 1 Hydrating agent
【表】
以上を均一に混合粉砕して水和剤とする。
使用に際しては、上記水和剤を水で50〜1000倍
に希釈して、有効成分量が10アール当り30〜1000
ｇになるように散布する。
配合例 ２
水溶液剤[Table] Mix and grind the above ingredients uniformly to make a wettable powder. When using, dilute the above hydrating agent 50 to 1000 times with water so that the amount of active ingredient is 30 to 1000 per 10 ares.
Spread it so that it becomes g. Formulation example 2 Aqueous solution
【表】
以上を完全に混合溶解して、水溶液剤とする。
使用に際しては、上記水溶液剤を水で50〜1000
倍に希釈して、有効成分量が10アール当り30〜
1000ｇになるように散布する。
試験例 １
莖葉処理による除草効果試験
縦15cm、横22cm、深さ６cmのプラスチツク製箱
に殺菌した洪積土壤を入れ、稲、メヒシバ、カヤ
ツリグサ、コアカザ、スベリヒユ、イヌガラシ、
ハキダメギク、トマト、キウリの種子を、それぞ
れスポツト状に播種し、約1.5cm覆土した。稲、
トマト、キウリおよび各種雑草が２〜３葉期に達
したとき、本発明化合物が100ｇ/aの割合となる
ように莖葉部へ散布した。
散布の際の薬液は前記配合例１の水和剤を水で
希釈し小型スプレーで、稲、トマト、キウリおよ
び各種雑草の莖葉部の全面に散布した。
薬液散布２週間後、稲、トマト、キウリおよび
各種雑草に対する除草効果を下記の判定基準に従
い調査した。
結果は、第２表に示す。
判定基準
５……殺草率90％以上
４……殺草率70〜90％
３……殺草率40〜70％
２……殺草率20〜40％
１……殺草率５〜20％
０……殺草率５％以下（ほとんど効力なし）
但し、上記の殺草率は、薬剤処理区の地上部生
草重および無処理区の地上部生草重を測定して下
記の式により求めたものである。
殺草率（％）＝（１−処理区の地上部生草重／無処理区の地上部生草重）×100[Table] Completely mix and dissolve the above ingredients to make an aqueous solution. When using, mix the above aqueous solution with water for 50 to 1000
When diluted twice, the amount of active ingredient is 30~ per 10 ares.
Spread to 1000g. Test Example 1 Herbicidal effect test by leaf pod treatment Put sterilized diluvial soil in a plastic box measuring 15 cm long, 22 cm wide, and 6 cm deep, and use it to test rice, crabgrass, cyperus, koakaza, purslane, dogfish, etc.
Seeds of leafminer, tomato, and cucumber were sown in spots and covered with soil about 1.5 cm. Rice,
When tomatoes, cucumbers, and various weeds reached the 2- to 3-leaf stage, the compound of the present invention was sprayed onto the leaf pods at a rate of 100 g/a. The chemical solution used for spraying was the hydrating agent of Formulation Example 1 diluted with water and sprayed using a small sprayer over the entire surface of the leaf buds of rice, tomatoes, cucumbers, and various weeds. Two weeks after spraying the chemical solution, the herbicidal effects on rice, tomatoes, cucumbers, and various weeds were investigated according to the criteria below. The results are shown in Table 2. Judgment criteria 5... Weed killing rate 90% or more 4... Weed killing rate 70-90% 3... Weed killing rate 40-70% 2... Weed killing rate 20-40% 1... Weed killing rate 5-20% 0... Killing Weed rate: 5% or less (almost no effect) However, the above weed killing rate was determined by measuring the weight of above-ground plants in the chemically treated area and the weight of above-ground plants in the non-treated area using the following formula. Weed killing rate (%) = (1 - above-ground grass weight in treated area / above-ground grass weight in untreated area) x 100
【表】【table】
【表】
試験例 ２
莖葉処理による除草効果試験
本発明化合物が25ｇ/a、12.5ｇ/a、6.3ｇ/aの
割合となるように莖葉部へ散布した。
散布の際の薬剤は、前記配合例２の水溶液剤を
水で希釈して、試験例１と同様にして試験を行な
つた。但し、綿の種子も、稲および各種雑草と同
様に播種して試験を行なつた。
除草効果は、試験例１に記載した判定基準に従
い調査した。
結果は第３表に示す。[Table] Test Example 2 Herbicidal effect test by treatment with pod leaves The compound of the present invention was sprayed on the pods at a rate of 25 g/a, 12.5 g/a, and 6.3 g/a. As for the chemical to be sprayed, the aqueous solution of Formulation Example 2 was diluted with water, and the test was conducted in the same manner as in Test Example 1. However, cotton seeds were also sown and tested in the same manner as rice and various weeds. The herbicidal effect was investigated according to the criteria described in Test Example 1. The results are shown in Table 3.
【表】【table】
【表】
第３表の如く、本発明化合物は綿に対して、殺
草効力はほとんどないという特色を有している。
試験例 ３
土壤処理による除草効果試験
縦15cm、横22cm、深さ６cmのプラスチツク製箱
に、殺菌した洪積土壤を入れ、稲、ノビエ、メヒ
シバ、カヤツリグサ、コアカザ、スペリヒユ、イ
ヌガラシ、ハキダメギクを混播し、約1.5cm覆土
した後、本発明化合物が100ｇ/a、の割合となる
ように土壤表面に散布した。
散布の際の薬液は、前記配合例１の水和剤を水
で希釈して小型スプレーで全面に散布した。
薬液散布３週間後に稲および各種雑草に対する
除草効果を試験例１に記載した判定基準に従い調
査した。
結果は第４表に示す。[Table] As shown in Table 3, the compounds of the present invention are characterized by having almost no herbicidal effect on cotton. Test Example 3 Weeding effect test using soil treatment A sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 cm wide, and 6 cm deep, and rice, wild grass, crabgrass, cyperus, koakaza, spermica, staghorn grass, and leafminer were mixedly sown. After covering the soil with approximately 1.5 cm of soil, the compound of the present invention was sprinkled onto the surface of the soil at a rate of 100 g/a. The chemical solution used for spraying was the wettable powder of Formulation Example 1 diluted with water and sprayed over the entire surface with a small sprayer. Three weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria described in Test Example 1. The results are shown in Table 4.
【表】
試験例 ４
多年生雑草に対する莖葉処理による除草効果試
験
チガヤ、ギシギシ、ジヨンソングラス、ヨモ
ギ、ハマスゲおよびキシユウスズメノヒエのそれ
ぞれの地上莖、塊根を野外で採取して、チガヤ、
ギシギシは1/5000アールのワグネルポツトに、ジ
ヨンソングラス、ヨモギ、ハマスゲは５寸鉢に、
キシユウスズメノヒエは縦15cm、横22cm、深さ６
cmのプラスチツク製箱に、それぞれ移植し、45〜
90日間温室内で充分生育させた後、本発明化合物
および対照化合物が単位面積当り所定の割合にな
るように、上記多年生雑草の莖葉部へ散布した。
散布の際の薬液は、前記配合例２の水溶液剤を
水で希釈し小型スプレーで雑草の莖葉部の全面に
散布した。
薬液散布１ケ月後、上記多年生雑草に対する除
草効果を試験例１に記載した判定基準に従い調査
した。
結果は第５表に示す。
この除草効果（殺草率）の調査後、それぞれの
雑草の地上部生草の部分を完全に切除して後、１
ケ月目に雑草の再生率について、下記の判定基準
に従い調査した。
結果は第５表に示す。
判定基準
５……再生率10％以下
４……再生率10〜30％
３……再生率30〜60％
２……再生率60〜80％
１……再生率80〜95％
０……再生率95％以上（薬剤無処理区とほぼ同
じ）
但し、上記の再生率は、調査時における薬剤処
理区の地上部生草重および無処理区の地上部生草
重を測定して、下記の式により求めたものであ
る。
再生率(%)＝（処理区の地上部生草重／無処理区の地上
部生草重）×100[Table] Test Example 4 Herbicidal effect test of perennial weeds by leaf pod treatment Ground pods and tuberous roots of Chigaya japonica, Jishigishi, Jyongson grass, Mugwort, Mugwort, Japanese commonweed, and Psyllium japonica were collected in the field.
Squirrel is placed in a 1/5000 are Wagner pot, and Jiyeonson Grass, mugwort, and Japanese knotweed are placed in a 5 inch pot.
Kisyuususumenohie is 15cm long, 22cm wide, and 6cm deep.
Transplant each into a plastic box of 45 cm
After sufficient growth in a greenhouse for 90 days, the compound of the present invention and the control compound were sprayed onto the leaf buds of the perennial weeds at a predetermined ratio per unit area. The chemical solution used for spraying was the aqueous solution of Formulation Example 2 diluted with water and sprayed over the entire surface of the weed pods using a small sprayer. One month after spraying the chemical solution, the herbicidal effect on the perennial weeds was investigated according to the criteria described in Test Example 1. The results are shown in Table 5. After investigating this herbicidal effect (weed killing rate), after completely cutting out the above-ground grass part of each weed,
The regeneration rate of weeds was investigated on the second month according to the following criteria. The results are shown in Table 5. Judgment criteria 5... Playback rate 10% or less 4... Playback rate 10-30% 3... Playback rate 30-60% 2... Playback rate 60-80% 1... Playback rate 80-95% 0... Playback The regeneration rate above is 95% or more (almost the same as the non-chemical treatment area). However, the above regeneration rate was determined by measuring the above-ground grass weight in the chemical-treated area and the above-ground grass weight in the non-treatment area at the time of the survey. It was calculated using the formula. Regeneration rate (%) = (Above-ground grass weight in treated area / Above-ground grass weight in untreated area) x 100
【表】【table】
【表】
第５表の如く、対照化合物のパラコートは、地
上部の殺草力は強いが、地下部への作用は弱く、
多年生雑草の再生を抑制する効力が弱いという欠
点を有している。一方、本発明化合物は、多年生
雑草に対する強い殺草力と同時に、地下部へも作
用し、雑草の再生を抑制する効力が極めて強いと
いう特色を有している。[Table] As shown in Table 5, the control compound, paraquat, has strong herbicidal power above ground, but has a weak effect on underground parts.
It has the disadvantage of being weak in suppressing the reproduction of perennial weeds. On the other hand, the compound of the present invention is characterized by its strong herbicidal activity against perennial weeds, as well as by its ability to act underground as well, and to have an extremely strong effect in suppressing weed regrowth.
Claims (1)
キル基を示し、Ｘは、水素原子、低級アルキル
基、ハロゲン原子またはアミノ基を示し、ｎは１
または２を示す。〕 で示されるＮ−ピリジル−アミノメチレンジホス
ホン酸系化合物の１種または２種以上を有効成分
として含有することを特徴とする除草剤。[Claims] 1. General formula [In the formula, R 1 , R 2 , and R 3 represent a hydrogen atom or a lower alkyl group, X represents a hydrogen atom, a lower alkyl group, a halogen atom, or an amino group, and n represents 1
or 2. ] A herbicide characterized by containing one or more N-pyridyl-aminomethylene diphosphonic acid compounds as an active ingredient.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8609877A JPS5437830A (en) | 1977-07-20 | 1977-07-20 | N-pyridyl-aminomethylenediphosphonic acid type herbicides |
| BR7804629A BR7804629A (en) | 1977-07-20 | 1978-07-18 | N-PYRIDYL-AMINO-METHYLENE-DIPHOSPHONIC ACID COMPOUNDS, HERBICIDES THAT CONTAIN THE SAME AND PROCESS FOR THEIR PRODUCTION |
| GB7830174A GB2004888B (en) | 1977-07-20 | 1978-07-18 | Hericides |
| DE19782831578 DE2831578A1 (en) | 1977-07-20 | 1978-07-18 | N-PYRIDYLAMINOMETHYLENIPHOSPHONIC ACID COMPOUNDS |
| IL55166A IL55166A (en) | 1977-07-20 | 1978-07-18 | N-pyridylaminomethylene-diphosphonic acid compounds,herbicides containing them and process for production thereof |
| IT50370/78A IT1156867B (en) | 1977-07-20 | 1978-07-19 | N-PYRIDYL-AMINO-METHYL-DIPHOSPHONIC ACID COMPOUNDS HERBICIDES THAT CONTAIN THEM AND PROCEDURE TO PRODUCE THEM |
| FR7821480A FR2398073A1 (en) | 1977-07-20 | 1978-07-20 | N-PYRIDYLAMINOMETHYLENE-DIPHOSPHONIC ACID DERIVATIVES, HERBICIDES CONTAINING THEM AND PROCESS FOR THE PREPARATION OF THE LATTER |
| US06/173,357 US4447256A (en) | 1977-07-20 | 1980-07-29 | N-(Unsubstituted or substituted pyridyl)aminomethylene-diphosphonic acids, herbicidal compositions containing same, their use for herbicides, and process for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8609877A JPS5437830A (en) | 1977-07-20 | 1977-07-20 | N-pyridyl-aminomethylenediphosphonic acid type herbicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5437830A JPS5437830A (en) | 1979-03-20 |
| JPS6113441B2 true JPS6113441B2 (en) | 1986-04-14 |
Family
ID=13877221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8609877A Granted JPS5437830A (en) | 1977-07-20 | 1977-07-20 | N-pyridyl-aminomethylenediphosphonic acid type herbicides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5437830A (en) |
-
1977
- 1977-07-20 JP JP8609877A patent/JPS5437830A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5437830A (en) | 1979-03-20 |
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