JPS5948481A - Hydantoin derivative and herbicide containing said derivative as active component - Google Patents

Hydantoin derivative and herbicide containing said derivative as active component

Info

Publication number
JPS5948481A
JPS5948481A JP57158228A JP15822882A JPS5948481A JP S5948481 A JPS5948481 A JP S5948481A JP 57158228 A JP57158228 A JP 57158228A JP 15822882 A JP15822882 A JP 15822882A JP S5948481 A JPS5948481 A JP S5948481A
Authority
JP
Japan
Prior art keywords
formula
compound
atom
derivative
weeds
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.)
Pending
Application number
JP57158228A
Other languages
Japanese (ja)
Inventor
Shizuo Shimano
静雄 島野
Shinichi Kobayashi
伸一 小林
Mikio Yanagi
柳　幹夫
Kura Yamada
蔵 山田
Mikio Saito
斉藤　三樹男
Fumio Nitani
二谷　文夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP57158228A priority Critical patent/JPS5948481A/en
Priority to ZA836359A priority patent/ZA836359B/en
Priority to AU18506/83A priority patent/AU563282B2/en
Priority to US06/527,493 priority patent/US4531964A/en
Priority to IL69615A priority patent/IL69615A/en
Priority to CA000436085A priority patent/CA1210766A/en
Priority to DK407283A priority patent/DK407283A/en
Priority to HU833173A priority patent/HU192160B/en
Priority to KR1019830004272A priority patent/KR840006242A/en
Priority to BR8304926A priority patent/BR8304926A/en
Priority to EP83108992A priority patent/EP0104532B1/en
Priority to AT83108992T priority patent/ATE24004T1/en
Priority to DE8383108992T priority patent/DE3368060D1/en
Publication of JPS5948481A publication Critical patent/JPS5948481A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/60—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

NEW MATERIAL:The hydantoin derivative of formula 1 (R1 is H or galogen; R2 is halogen; R3 is H or 1-8C straight or branched-chain alkyl which may be substituted with lower alkoxy; X is O or S; n is 3 or 4). EXAMPLE:3-( 4-Chloro-3-n-propoxycarbonylphenyl )-1,5-trimethylene-2-thiohydantoin. USE:Herbicide remarkably effective not only to the annual weeds in paddy field, e.g. Deccan grass and broad-leaved weeds, etc., but also to the perennial weeds such as slender spikerush, etc. PROCESS:The compound of formula 1 can be prepared by (1) reacting the proline or pipecolic acid or its eater of formula 2 (R4 is H or lower alkyl; n is 3 or 4) with the substituted-phenyl isocyanate of formula 3, and (2) heating the resultant compound of formula 4 or cyclizing the compound in the presence of a proper acidic catalyst.

Description

【発明の詳細な説明】 本発明は式 （式中、Ｒ，は水素原子またはハロゲン原子を、Ｒ２は
ハロゲン原子を、■ｔ３は水素原子または低級アルコキ
シ基によって置換されていてもよいＣ２〜Ｃ８の直鎖ま
たは枝分れのアルキル基を、Ｘは酸素原子またはイオウ
原子を表わし、１］は３又は４の整数を表わす） で示されるヒダントイン誘導体およびそれを有効成分と
して含有することを特徴とする除草剤に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula (wherein R is a hydrogen atom or a halogen atom, R2 is a halogen atom, and a straight-chain or branched alkyl group, X represents an oxygen atom or a sulfur atom, and 1] represents an integer of 3 or 4), and contains the same as an active ingredient. This relates to herbicides.

ヒダントイン誘導体の中には、除草活性を有２４２があ
げられる。Among the hydantoin derivatives, there are 242 that have herbicidal activity.

本発明者等はＮ−置換フェニルのヒダントイン誘導体に
ついて種々検討を重ねた結果式（１）で示される如くパ
ラ位に・・ロゲン原子を有し、メタ位にカルボキシル基
又はそのエステル基を有する誘導体が驚くべきことに極
めて強力な除草活性を示し、しかも作物に対する薬害も
少なく実用的な除草剤となりうろことを見い出し本発明
を完成するにいたった。The present inventors have conducted various studies on hydantoin derivatives of N-substituted phenyl, and as a result, as shown in formula (1), a derivative having a rogen atom at the para position and a carboxyl group or its ester group at the meta position. Surprisingly, it was discovered that this herbicide exhibits extremely strong herbicidal activity and has little phytotoxicity to crops, making it a practical herbicide, leading to the completion of the present invention.

本発明化合物は、水田のヒエ類や広葉雑草等−年生雑草
に対して低薬量ですぐれた除草効力を示すのみならず、
ミズガヤツリ、ホタルイ、クログアイ、マツバイ、ウリ
カワ等多年生雑草に対しても強い除草効力を示し、また
畑地においても発芽前処理、生育期処理に於いてすぐれ
れ除草効力を示し、特にヒュ科、アカザ科、タデ科等の
広葉雑草に対しては低薬量で極めてずぐれた除草効力を
有することを発見した。他方イネ、小麦、エンバク、ト
ウモロコシ、ダイス、等の作物に対する薬害は少なく、
実用性ある除草剤として有用である。The compound of the present invention not only exhibits excellent herbicidal efficacy against annual weeds such as barnyard grass and broad-leaved weeds in paddy fields at a low dose;
It also shows a strong herbicidal effect on perennial weeds such as cypress, bulrush, black eye, pineweed, and weed, and also shows excellent herbicidal effect in fields during pre-emergence treatment and treatment during the growing season. It was discovered that it has extremely excellent herbicidal efficacy against broad-leaved weeds such as Polygonaceae at a low dose. On the other hand, there is little phytotoxicity to crops such as rice, wheat, oats, corn, and dices.
It is useful as a practical herbicide.

式（１）で示されるヒダントイン誘導体は例えば以下に
示すように式（２）（式中Ｉｔ、は水素原子または低級
アルキル基を、ｎは３又は４の整数を表０（４） リ　　しＵ わす）で示されるプロリンまたはピペコリン酸あるいは
それらのエステルと式（３）（式中Ｉｔ、　、　ＬＬ、
　。The hydantoin derivative represented by formula (1) is, for example, represented by formula (2) as shown below (in the formula, It represents a hydrogen atom or a lower alkyl group, and n represents an integer of 3 or 4, as shown in Table 0(4)). proline or pipecolic acid or their esters represented by formula (3) (in the formula It, , LL,
.

Ｉモ３およびＸは式（１）に同じ）で示される置換フェ
ニルイソシアネートまたは置換フェニルインチオシアネ
ートとを反応させて、式（４）（式中＋４．　。Imo3 and X are the same as in formula (1)) are reacted with a substituted phenyl isocyanate or a substituted phenyl inthiocyanate represented by formula (4) (in the formula +4.

１１．２．Ｈ・３．Ｘ、　Ｉｔ４は式（１）に同じ）で
示される化合物を得、そのまま反応を継続させるかまた
は式（３）の化合物をとりだしてもよいが、得られた化
合物を加熱処理するかまたは適当な酸触媒を加えろこと
により環化して式（１）で示される化合物を得ることが
できる。反応は無溶媒でも行うことができるが、一般的
には不活性溶媒を用いるのが好ましく、反応温度は通常
ＯＣ〜１５０Ｃで実施するが、Ｘが酸素原子の場合は通
常ＯＣ〜５０Ｃで式（４）の化合物が得られ、それ以上
の温度に加熱すると環化する場合が多いが、酸触媒を加
えると容易に環化することができる。、脣たＸがイオウ
原子の場合も同様に環化することができる。反応時間は
通常３０分から３時間程度である。11.2. H.3. X, It4 is the same as in formula (1)), and the reaction may be continued as it is, or the compound of formula (3) may be taken out, but the obtained compound may be heat-treated or subjected to an appropriate treatment. By adding an acid catalyst, the compound represented by formula (1) can be obtained by cyclization. Although the reaction can be carried out without a solvent, it is generally preferable to use an inert solvent, and the reaction temperature is usually carried out at OC to 150C, but when X is an oxygen atom, it is usually carried out at OC to 50C with the formula ( The compound 4) is obtained, which often cyclizes when heated to a higher temperature, but can be easily cyclized by adding an acid catalyst. , When X is a sulfur atom, cyclization can be performed in the same manner. The reaction time is usually about 30 minutes to 3 hours.

不活性溶媒としてはベンゼン、トルエン、キシレン、ク
ロロベンゼンなどの芳香族炭化水素類；　ｎ−ヘキサン
、１］−ヘプタン、石油エーテルなどの脂肪族炭化水素
類；ンクロヘキザンなどの脂環式炭化水素類；クロロポ
ルム、四塩化炭素類；パークレンなどのノ・ロゲン化炭
−化水素類；アセトン、メチルエチルケトンなどのケト
ン類；エチルエーテル、テトラヒドロフラン、ジオキサ
ンなどのエーテル類；メタノール、エタノールなどのア
ルコール類；酢酸エチルエステルナトのエステル類；ジ
メチルホルムアミドなどのアミド類首たは水等が用いら
れる３、酸触媒としてはｐ−１−ルエンスルホン酸、硫
酸、塩化水素等が用いられる。Examples of inert solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as n-hexane, 1]-heptane, and petroleum ether; alicyclic hydrocarbons such as nclohexane; and chloroporm. , carbon tetrachloride; non-logenated hydrocarbons such as perchloren; ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, tetrahydrofuran, and dioxane; alcohols such as methanol and ethanol; acetic acid ethyl ester sodium esters; amides such as dimethylformamide, water, etc. are used; as acid catalysts, p-1-luenesulfonic acid, sulfuric acid, hydrogen chloride, etc. are used.

式（１）において・・ロゲン原子の例としては塩素、臭
素、フッ素等をあけることができる。In formula (1), chlorine, bromine, fluorine, etc. can be used as examples of rogen atoms.

低級アルコキシ基の例としてはメトキシ、エトキシ等の
基をあげることができる。Examples of lower alkoxy groups include groups such as methoxy and ethoxy.

０１〜Ｃ８の直鎖または枝分れのアルキル基の例として
はメチル、エチル、ｎ−プロピル、】−プロピル、ｎ−
ブチル、Ｓ−ブチル、１−ブチル、ｎ−ペンチル、０−
ヘキシル、＋１−ヘプチル、ｎ−オクチル、２−エチル
ヘキシル、■＋３−ジメチルブチル等の基をあげること
ができる。Examples of straight chain or branched alkyl groups of 01 to C8 are methyl, ethyl, n-propyl, ]-propyl, n-
Butyl, S-butyl, 1-butyl, n-pentyl, 0-
Examples include groups such as hexyl, +1-heptyl, n-octyl, 2-ethylhexyl, and +3-dimethylbutyl.

式（４）において＋１４で示される低級アルキル基の例
としてはＣ１〜Ｃ４の直鎖または枝分れのアルキル基を
あげることができ、その例としては、メチル、エチル、
ロープロピル、ｉ−プロピル、１１−ブチル、Ｓ−ブチ
ル等の基をあげることができる。Examples of the lower alkyl group represented by +14 in formula (4) include C1 to C4 linear or branched alkyl groups, such as methyl, ethyl,
Examples include groups such as lopropyl, i-propyl, 11-butyl, and S-butyl.

原料である式（２）で示される化合物は公知化合物であ
る。また式（３）で示される化合物は式（５）（７） （式中１も、　、　１１，２．　Ｒ，３は式（１）に同
じ）で示される置換アニリン類と式（６）（式中Ｘは酸
素原子またはイオウ原子を、Ｙは）・ロゲン原子を表わ
す）で示されるホスゲン捷たはチオホスゲンあるいは式
（７）で示されるトリクロロメチルクロロホルメートと
反応させることにより得ることができる。The compound represented by formula (2), which is a raw material, is a known compound. Further, the compound represented by formula (3) is a substituted aniline represented by formula (5) (7) (wherein 1 is also , 11, 2. R, 3 are the same as in formula (1)) and formula (6) (In the formula, X represents an oxygen atom or a sulfur atom, and Y represents a can.

反応は無溶媒で行うことができるが望捷しくは不活性溶
剤を用い、一般的には一２０Ｃと混合物の沸点との間で
実施され、望捷しくはＯＣ〜１２０Ｃの間で実施される
。寸だ、反応は常圧の下でおこなうのが重重しいが、加
圧剤たは減圧下で操作することも可能である８ 次に本発明の合成例について具体的に説明する。The reaction can be carried out without a solvent, but preferably with an inert solvent, and is generally carried out between -20C and the boiling point of the mixture, preferably between OC and 120C. . Although it is difficult to carry out the reaction under normal pressure, it is also possible to carry out the reaction using a pressurizing agent or under reduced pressure.8 Next, synthesis examples of the present invention will be specifically explained.

合成例］、、　　３−（４−クロロ−３−ノルマルプロ
ポキシカルボニルフェニル）−１，５−）リメチレンー
２−チオヒダントイン（化合物嘔１）プロリンエチルエ
ステル１．５Ｆ−（０，０１モル）をベンゼン３０ｍ１
：に溶解し４−クロロ−３−／　ノｌ／マルグロボキシ
カルポニルフェニルインチオシアネート２．６　ｙ−（
０，’０１モル）を加え、室温にて１時間攪拌したのち
、濃縮して得られる油状物をシリカゲルカラムクロマト
グラフィーで不肖製１−ると淡黄色結晶１．６Ｐ（収率
４５％）の目的物を得た。Synthesis example] 3-(4-chloro-3-n-propoxycarbonylphenyl)-1,5-)limethylene-2-thiohydantoin (compound 1) proline ethyl ester 1.5F-(0.01 mol) was dissolved in benzene. 30m1
: Dissolved in 4-chloro-3-/nol/margloboxycarponylphenylthiocyanate 2.6y-(
After stirring at room temperature for 1 hour, the oily substance obtained by concentration was subjected to silica gel column chromatography to obtain pale yellow crystals of 1.6P (yield: 45%). Obtained the object.

融点は９３〜９５ｔＺ’を示した。The melting point was 93-95tZ'.

元素分析値　ＣＩ６１１１７　ｃｌ　Ｎ２０３　Ｓ泪　
　算　　値　　Ｃ：５４．４６　１１：４．８５　　Ｎ
ニア、９３実　　測　　値　　Ｃ：５４．７／Ｉ　　　
Ｉｌ：４．９４　　Ｎ：８．０５プロリンエチルエステ
ルの代りにプロリンエチルエステル塩酸塩を用いてもト
リエチルアミンを使用することにより同様に目的物を得
ることができる。Elemental analysis value CI61117 cl N203 S tears
Calculation value C: 54.46 11: 4.85 N
Near, 93 actual measurement value C: 54.7/I
Il: 4.94 N: 8.05 Even if proline ethyl ester hydrochloride is used instead of proline ethyl ester, the desired product can be similarly obtained by using triethylamine.

合成例２ ３−（２−フロロ−４−クロロ−５−インプロポキシカ
ルボニルフェニル）−１，５−テトラメチレンヒダノド
イン（化合物ＮＬ１７　）ピペコリン酸エチルエステル
３．２９−　（０，０２モル）ヲベンゼン３０ｍ１に溶
解し、２−フ四ロー１１−クロロー５−１’ソプロボキ
シカルボニルフェニルイソノアネート５．１５１００２
モル）を加え４０〜５０Ｃで１時間加熱攪拌する。その
後水洗し、無水硫酸ナトリウムで乾燥し、濃縮して得ら
れる結晶をｎ−へキサンと酢酸エチルの混合液で再結晶
−すると１−（２−フロロ−７１−クロロ−５−イソプ
ロポキシカルボニルフェニル）アミノカルボニル−２−
工トキシカルボニルピペリジン６９Ｉ（収率８３２％）
が得られる。この化合物４□ｏ、ｏｏ９６モル）をトル
エン７０　ｍｌに溶角イし塩化水素を吹き込み、室温に
て：３時間侵４１ニジたのち炭酸水素ナトリウト飽和水
溶液で洗浄し、水洗したのち無水硫酸ナトリウムで乾燥
後グ３縮してイｓＩられる結晶をトルエンとｌｌｉ’Ｅ
ｆｆエチルの混合液から再結晶すると白色結晶２．６　
ｇ−（収率７１０％）の目的物を得た。融点は１２８〜
１２９Ｃを示した。Synthesis Example 2 3-(2-fluoro-4-chloro-5-impropoxycarbonylphenyl)-1,5-tetramethylenehydanodoin (compound NL17) pipecolic acid ethyl ester 3.29- (0.02 mol) benzene 30 ml Dissolved in 2-chloro-11-chloro-5-1'soproboxycarbonylphenylisonoanate 5.151002
mol) and stirred while heating at 40-50C for 1 hour. Thereafter, the crystals obtained by washing with water, drying with anhydrous sodium sulfate, and concentrating are recrystallized from a mixture of n-hexane and ethyl acetate to produce 1-(2-fluoro-71-chloro-5-isopropoxycarbonylphenyl). )aminocarbonyl-2-
Toxicarbonylpiperidine 69I (yield 832%)
is obtained. This compound (4□o, oo, 96 mol) was dissolved in 70 ml of toluene, hydrogen chloride was blown into the solution, and after immersion at room temperature for 3 hours, the mixture was washed with a saturated aqueous solution of sodium bicarbonate, water, and anhydrous sodium sulfate. After drying, the crystals obtained by condensation are mixed with toluene.
When recrystallized from a mixture of ff ethyl, white crystals 2.6
g-(yield 710%) of the target product was obtained. Melting point is 128~
It showed 129C.

元素分析値　Ｃ＋７Ｒｇ　Ｉ”　ＣＩ　Ｎ２０４泪　　
算　　値　　Ｃ：５５．３６　１１：４．９１　　Ｎニ
ア、５９実　　　４１月　　　イ直　　　Ｃ二　５５．
５８　　１１：　　／１．８６　　　Ｎニア、７０合成
例３ ３−（４−クロロ−３−メトキシカルボニルジェニル）
　−１’、　５−テトラメチレン−２−チオヒダントイ
ン（化合物ｒＩＩｔｉ　１０　）ピペコリン酸エチルエ
ステル１．６　＃　（０，（１１モル）をベンゼン３０
ｍｅに溶解し／Ｉ−クロ「１〜：ウ一メトキシカルボニ
ルフェニルインチオシアネート２．３　Ｐ　（０，０１
モル）を加え、室温にて１時間攪拌したのち、濃縮して
得られる結晶をトルエンと酢酸エチルエステルの混合液
から再結晶すると淡黄色結晶２．４　Ｌｉ／−（収率７
１％）の目的物を得た。Elemental analysis value C+7Rg I” CI N204 Tears
Calculated value C: 55.36 11: 4.91 N near, 59 fruit 41 month I direct C two 55.
58 11: /1.86 Nia, 70 Synthesis Example 3 3-(4-chloro-3-methoxycarbonylgenyl)
-1', 5-tetramethylene-2-thiohydantoin (compound rIIti 10 ) pipecolic acid ethyl ester 1.6 # (0, (11 mol)) in benzene 30
Dissolved in me/I-chloro'1~: U-methoxycarbonylphenylthiocyanate 2.3 P (0,01
After stirring at room temperature for 1 hour, the resulting crystals were recrystallized from a mixture of toluene and acetic acid ethyl ester to give pale yellow crystals of 2.4 Li/- (yield: 7
1%) of the target product was obtained.

融点は１６７〜１６９Ｃを示した。The melting point was 167-169C.

元素分析値　Ｃ＋、ｔ　１−１＋５　Ｃ’ｌ　Ｎ２０３
Ｓ計算値Ｃ：５３．１７　Ｊ−Ｉ：４．４６　Ｎ：８．
２６実　　測　　値　　Ｃ：５３．３９　　）Ｉ：４．
４４　　Ｎ＋８．１４合成例４゜ ３−（２−フロロ−４−クロロ−５−セカンダリ−ブト
キシカルボニルフェニル）−１，５−テ）ジメチレン−
２−チオヒダントイン（化合物Ｎ１１１６）−ピペコリ
ン酸エチルエステル２．１７（０，０１３９モル）をベ
ンゼン３０ｍ１に溶解Ｌ２−フロロー４−クロロー５−
セカンダリ−ブトキシフェニルイソチオシアネート４ｆ
ｉ’−（０，０１３９モル）を加え、室温にて１時間攪
拌したのち、水洗し、無水硫酸すＩ−’Ｊウムで乾燥後
濃縮して得られる油状物をシリカゲルカラムクロマトグ
ラフィーで精製すると淡褐色結晶３．３７（収率５ｇ、
ｓ％）の目的物を・得た。融点は８６〜８８Ｃを示した
。Elemental analysis value C+, t 1-1+5 C'l N203
S calculated value C: 53.17 J-I: 4.46 N: 8.
26 Actual measurement value C: 53.39) I: 4.
44 N+8.14 Synthesis Example 4゜3-(2-Fluoro-4-chloro-5-secondary-butoxycarbonylphenyl)-1,5-te)dimethylene-
2-Thiohydantoin (compound N1116)-pipecolic acid ethyl ester 2.17 (0,0139 mol) was dissolved in 30 ml of benzene L2-fluoro4-chloro5-
Secondary butoxyphenyl isothiocyanate 4f
After adding i'-(0,0139 mol) and stirring at room temperature for 1 hour, washing with water, drying with anhydrous sulfuric acid, and concentrating, the obtained oil was purified by silica gel column chromatography. Light brown crystal 3.37 (yield 5g,
s%) of the target product was obtained. The melting point was 86-88C.

元素分析値　Ｃｌ８ＩＩ２ｏ１−ＣＩＮ２０３Ｓ計算値
Ｃ：５４．２０　Ｉ］コ５．０５　Ｎ’ニア、６２実　
　測　　値　　Ｃ：５４．４２　　Ｈ：５．１２　　Ｎ
ニア、０３合成例５ ３−（２−フロロ−４−クロロ−５−メトキシエトキシ
カルボニルフェニル）　−１，５−テトラメチレン−２
−チオヒダントイン（化合物Ｎｕ　’１９　）ピペコリ
ン酸エチルエステル３．２　ｇ−（０，０２モル）をベ
ンゼア　５０　ｍｅに溶解し２−フロロ−４−クロロ−
５−メトキシエトキシカルボニルフェニルイソチオシア
ネート５．８５’（０，０２モル）を加え４０〜５０Ｃ
で１時間加熱攪拌したのち水洗し、無水硫酸すトリウム
で乾燥後、濃縮して得られる油状物をシリカゲルカラム
クロマトグラフィーで精製すると淡褐色油４．６　ｇ−
（収率５７．４％）の目的物を得た。屈折率はｎ　ｏ５
１．５７２９を示した。Elemental analysis value Cl8II2o1-CIN203S calculated value C: 54.20 I] 5.05 N' near, 62 real
Measured value C: 54.42 H: 5.12 N
Near, 03 Synthesis Example 5 3-(2-fluoro-4-chloro-5-methoxyethoxycarbonylphenyl)-1,5-tetramethylene-2
-Thiohydantoin (compound Nu'19) pipecolic acid ethyl ester 3.2 g (0.02 mol) was dissolved in benzea 50 me and 2-fluoro-4-chloro-
Add 5-methoxyethoxycarbonylphenyl isothiocyanate 5.85' (0.02 mol) to 40-50C
After heating and stirring for 1 hour, the oil was washed with water, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography to give 4.6 g of light brown oil.
The desired product was obtained (yield 57.4%). The refractive index is no5
It showed 1.5729.

元素分析値　Ｃｌ７１１ｔａ　Ｆｃｌ　Ｎ２０４Ｓ計算
値Ｃ：５０．９４１（：／１．５３　Ｎ：６．９８実　
　測　　値　　Ｃ：５１．０７　１−１：４．４５　　
Ｎニア、２１上記の方法により得られる化合物の例を第
１表にあげる。Elemental analysis value Cl711ta Fcl N204S calculated value C: 50.941 (:/1.53 N: 6.98 real
Measured value C:51.07 1-1:4.45
Nia, 21 Examples of compounds obtained by the above method are listed in Table 1.

第１表 次に式（３）で示される置換フェニルイソシアネートお
よび置換フェニルインチオシアネートの合成について具
体的に説明する。Table 1 Next, the synthesis of substituted phenyl isocyanate and substituted phenyl inthiocyanate represented by formula (3) will be specifically explained.

参考列１．４−クロロー２−フロロ−５−インプロポキ
シカルボニルフェニルイソシアネートの製造 トリクロロメチルクロロホルメート５．４　ｍｌ（０，
０４５モル）を酢酸エチル３０ｍｅに加え、ＯＣに冷却
した後、この溶液に４−クロロ−２−フロロ−５−イソ
プロポキシカルボニルアニリン１３．９グ；（０，０６
モル）を酢酸エチル２５ｍ１とからなる溶液を１５分間
で滴下する。０〜１０Ｃで１時間攪拌した後、２時間還
流部度に保つ。その後濃縮すると目的物１５．４５７（
収率９９．９％）が融点４１〜４３Ｃの類白色結晶とし
て得られる。Reference row 1. Preparation of 4-chloro-2-fluoro-5-impropoxycarbonylphenyl isocyanate Trichloromethyl chloroformate 5.4 ml (0,
After cooling to OC, 13.9 g of 4-chloro-2-fluoro-5-isopropoxycarbonylaniline;
mol) and 25 ml of ethyl acetate was added dropwise over 15 minutes. After stirring for 1 hour at 0-10C, keep at reflux for 2 hours. Then, when concentrated, the target product 15.457 (
(Yield 99.9%) is obtained as off-white crystals with a melting point of 41-43C.

参考例２．　２．４−ジクロロ−５−エトキシカルボニ
ルフェニルインチオシアネートの製造２．４−シクロロ
ー５−エトキシカルボニルアニリン２３．４ｆＦ（０，
１モル）をりｏｏホ／Ｌ／　ム８０　ｍｌに溶解し、１
０Ｃ以下に冷却後、チオホスゲン１４．９　、％（０，
１３モル）を滴下し、室温にて２時間攪拌後還流３時間
行ったのち、濃縮すると淡褐色結晶２７ｇ−（収率９７
．７％）の目的物を得る。Reference example 2. 2. Preparation of 4-dichloro-5-ethoxycarbonylphenyl thiocyanate 2.4-cyclo-5-ethoxycarbonylaniline 23.4 fF (0,
Dissolve 1 mol) in 80 ml of Riooho/L/mu,
After cooling to below 0C, thiophosgene 14.9% (0,
13 mol) was added dropwise, stirred at room temperature for 2 hours, refluxed for 3 hours, and concentrated to give 27 g of light brown crystals (yield: 97
．． 7%) of the desired product.

融点は４５〜４６Ｃを示した。The melting point was 45-46C.

本発明化合物を除草剤の有効成分として使用する場合、
本発明化合物を１種または２種以上を使用してもよい。When using the compound of the present invention as an active ingredient of a herbicide,
One type or two or more types of the compounds of the present invention may be used.

本発明化合物を除草剤に使用する場合、使用目僧に応じ
てそのままか、または効果を助長あるいは安定にするた
めに農薬補助剤を混用して、農薬製造分野において一般
に行われている方法により粉剤、細粒剤、粒剤、水利剤
、フロアブル剤および乳剤等の製造形態にして使用する
ことができる。When the compound of the present invention is used as a herbicide, depending on the purpose of use, it may be used as it is, or it may be mixed with an agrochemical adjuvant to enhance or stabilize the effect, and it may be made into a powder by a method commonly used in the field of agrochemical manufacturing. It can be used in the form of manufacturing forms such as fine granules, granules, irrigation agents, flowable agents, and emulsions.

これらの種々の製剤は実際の使用に際しては、直接その
″ｉ！、捷使用するか、捷たは水で所望の濃度に希釈し
て使用することができる。In actual use, these various preparations can be used directly after dilution or diluted with dilution or water to a desired concentration.

ここに言う農薬補助剤としては担体（希釈剤）およびそ
の他の補助剤たとえば展着剤、乳化剤、湿展剤、分散剤
、固着剤、崩壊剤等をあげることができる。The agrochemical auxiliary agents mentioned herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants.

液体担体としてはトルエン、キシレン等の芳香族炭化水
素、メタノール、ブタノール、グリコール等のアルコー
ル類、アセトン等のケトン類、ジメチルホルムアミド等
のアミド類、ジメチルスルホキシド等のスルホキシド類
、メチルナフタレン、シクロヘキサン、動植物油、脂肪
酸、脂肪酸エステル等があげら゛れる。Liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animals and plants. Examples include oil, fatty acids, fatty acid esters, etc.

固体担体としてはクレー、カオリン、メルク、珪藻土、
シリカ、炭酸カルシウム、モンモリロナイト、ベントナ
イト、長石、石英、アルミナ、鋸屑等があげられる。Solid carriers include clay, kaolin, Merck, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, and sawdust.

また乳化剤域たは分散剤としては通常界面活性剤が使用
され、たとえば高級アルコール硫酸ナトリウム、ステア
リルトリメチルアンモニウムクロライド、ポリオキシエ
チレンアルキルフェニルエーテル、ラウリルベタイン等
の陰イオン系界面活性剤、陽イオン系界面活性剤、非イ
オン系界面活性剤、両性イオン系界面活性剤があげられ
る。In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cationic surfactants. Examples include activators, nonionic surfactants, and zwitterionic surfactants.

いずれの製剤もそのまま単独で使用できるのみならず殺
菌剤や殺虫剤、植物生長調節剤、殺ダニ剤、農園芸用殺
菌剤、土壌殺菌剤、土壌改良剤あるいは殺線虫剤と混合
してもよくさらに肥料や他の除草剤と混合して使用する
こともできる。All formulations can not only be used alone, but also mixed with fungicides, insecticides, plant growth regulators, acaricides, agricultural and horticultural fungicides, soil fungicides, soil conditioners, or nematicides. It can also often be used in combination with fertilizers and other herbicides.

本発明除草剤における有効成分化合物含量は、製剤形態
、施用する方法、その他の条件によって種々異なり、場
合によってはイ１効成分化合物のみでも′よいが、通常
は０．５〜９５　％　（Ｘ［吊：　）好ましくは２〜５
０％（重量）の範囲である。[ Hanging: ) Preferably 2-5
It is in the range of 0% (weight).

寸だ本発明除草剤で除草する場合、その使用ボは使用化
合物および適用場所等によって異なるが通常１アール当
り有効成分化合物が１〜ｔｏｏｙ好ましくは３〜７５　
Ｆ−の範囲で使用される。When weeding with the herbicide of the present invention, the number of active ingredients used varies depending on the compound used and the place of application, but the amount of active ingredient compound per area is usually 1 to too, preferably 3 to 75.
Used in the F- range.

次に本発明の製剤例についてさらに詳細に説明するが、
添加物の種類および混合比率はこれらのみに限定される
ことなく広い範囲で使用ｉｉＪ能である。なお、部とあ
るのは重量部をあられず。Next, formulation examples of the present invention will be explained in more detail.
The types and mixing ratios of additives are not limited to these, and can be used in a wide range. Note that parts do not refer to parts by weight.

製剤例１．乳　剤 化合物番号２の５０部にキシレンとメチルナフタレンの
混合物（１：１）３５部を加えて溶解しサラにポリオキ
シエチレンアルキルフェニルエーテルとアルキルベンゼ
ンスルボン酸カルシウムの混合物（８：２）１５部と混
合することにより乳剤が得られる。Formulation example 1. Add 35 parts of a mixture of xylene and methylnaphthalene (1:1) to 50 parts of emulsion compound No. 2, dissolve it, and add 15 parts of a mixture of polyoxyethylene alkylphenyl ether and calcium alkylbenzene sulfonate (8:2). An emulsion is obtained by mixing with.

製剤例２　粉　剤 化合物番号７の５部にクレー９５部を加え、混合粉砕す
ることにより粉剤が得られる。Formulation Example 2 Powder A powder is obtained by adding 95 parts of clay to 5 parts of Compound No. 7, mixing and pulverizing.

製剤例３．水利剤 化合物番号８の５０部を珪藻土１０部、カオリン；う２
部の１−４体と混合しさらにラウリル硫酸ナトリウムと
２，２′−ジナフチルメタンスルフオン酸ナトリウムの
混合物８部を均等に混合した後粉砕して微粉末とし水和
剤を得る。Formulation example 3. 50 parts of irrigation compound number 8, 10 parts of diatomaceous earth, 2 parts of kaolin
8 parts of a mixture of sodium lauryl sulfate and sodium 2,2'-dinaphthylmethane sulfonate were mixed evenly with 8 parts of the mixture and pulverized into a fine powder to obtain a wettable powder.

製剤例４１粒　剤 化合物番号１５の微粉末５部を適当な混合機を用いて珪
石粒（１６−３２メツシユ）９４．５部の上にポリ酢酸
ビニール０５部のメタノール溶液を結合剤として展着被
覆せしめて粒剤を得る。Formulation Example 41 Granules 5 parts of fine powder of Compound No. 15 was spread on 94.5 parts of silica grains (16-32 mesh) using a suitable mixer with a methanol solution of 0.5 parts of polyvinyl acetate as a binder. The mixture is coated to obtain granules.

以下に本発明の有効成分化合物がすぐれた除草活性を有
していることを実験例により説明する。The excellent herbicidal activity of the active ingredient compound of the present invention will be explained below using experimental examples.

実験は全て２連制でおこない、結果の数字は各々の平均
値を以って示したものである。All experiments were conducted in duplicate, and the results are shown as the average value of each.

実験例１　水田雑草発生前湛水下処理 １７５．０００アールのワグネルポノトに水田土壌を一
定量つめ植成状態とし、タイヌビエ、コナギ、キカシグ
サ、アゼナ、ミゾハコベ、クマガヤツリの種子の一定量
を播種した。さらにウリノ１ワの塊茎をポット当り３個
を土壌表層より１　ｃｍの深さに埋め込み、３ｃｍの深
さの湛水をおこなった後、本発明有効成分化合物がアー
ル当り６．２５！ｉ’〜５０１になるように調整した希
釈液を湛水中に滴下処理した。薬剤処理後３０日目に除
草効果を調査した。Experimental Example 1 Submergence treatment before the emergence of rice field weeds A certain amount of paddy soil was packed into a 175,000 are Wagner Ponot and planted, and a certain amount of seeds of Japanese millet, Japanese staghorn, Japanese cypress, azalea, Japanese chickweed, and Japanese cypress were sown. Furthermore, after embedding 3 tubers of Urino 1wa per pot to a depth of 1 cm below the soil surface and flooding to a depth of 3 cm, the active ingredient compound of the present invention was found to be 6.25 per pot! A diluted solution adjusted to i' ~ 501 was dropped into flooded water. The herbicidal effect was investigated 30 days after the chemical treatment.

なお調査は次の基準でおこない第２表の結果を得た。The investigation was conducted using the following criteria and the results shown in Table 2 were obtained.

※除幕効果指数 ５：完全除草 ４：８０％程度の除草 ３．６０％ ２：４０％ １コ２０’をン Ｏ：効力なし 第２表　実験例１　雑草発生前湛水下処理（ｉ　　考（
１１広　　　　　葉：コナギ、キカシグサ、アゼナ、ミ
ゾノ・コベ（２）カヤツリグサ：タマガヤツリ １ 実験例２　水田生育期湛水下処理 １１５．０００アールのワグネルポットに水田土壌を一
定量つめ植成状態とし、タイヌビエ、コナギキカシグサ
、アゼナ、ミゾハコベ、クマガヤツリの種子を一定量播
ｆ重した。さらにウリカワの塊茎をポット当り３個土壌
表層より１　ｃｍの深さに埋め込み、２．５葉期の水稲
苗（二ホンバレ）３本を移植した。３’ｃｍの深さの湛
水をおこない、温室内で生育させた。雑草が２〜３葉期
に生育した時に本発明有効成分化合物がアール当９６２
５〜２５　Ｆ−になるように調整した希釈ｉ−を湛水中
に滴下処理した。*Weeding effect index 5: complete weeding 4: about 80% weeding 3.60% 2: 40% 1/20' O: no effect Table 2 Experimental example 1 Submergence treatment before weed emergence (i Consideration)
11 Broad Leaves: Cyperus japonica, Cyperus japonica, Azena, Mizono kobe (2) Cyperus cyperus: Cyperus cyperus 1 Experimental example 2 Paddy growing season Submerged treatment A certain amount of paddy soil was filled in a 115,000 are Wagner pot and planted, and a certain amount of paddy soil was planted. A certain amount of seeds were sown at a certain weight. Furthermore, three Urikawa tubers were buried in each pot at a depth of 1 cm below the soil surface layer, and three paddy rice seedlings (Nihonbare) at the 2.5 leaf stage were transplanted. The plants were flooded to a depth of 3'cm and grown in a greenhouse. When weeds grow at the 2-3 leaf stage, the active ingredient compound of the present invention
Diluted i- adjusted to 5-25 F- was dropped into the flooded water.

薬剤処理後３０日目に除草効果を調査し第３表の結果を
得た。なお調査の糸鋸は除草効果については実験例１と
同じで、薬害については次の通りである。The herbicidal effect was investigated 30 days after the chemical treatment, and the results shown in Table 3 were obtained. The weeding effect of the investigated jig saw was the same as in Experimental Example 1, and the chemical damage was as follows.

※薬害指数 一二無　害　　州：中　害 ＋：僅小害　　　曲：甚　害 廿：小　害　　×　枯　死 第３表　実験例２　水田雑草生育期洪水下処理実験列１
および２の結果にみられるように本発明化合物は水田の
１年生、多年生の主要雑草に対し、発芽前後処理と生育
期処理ですぐれた除草効力を示した。しかも水稲に対し
ても高い安全性を示すことがわかった。*Pharmaceutical damage index 12 No Harm State: Moderate Harm +: Slight damage Song: Severe Harm: Slight Harm × Death Table 3 Experimental example 2 Paddy field weed growing season Flood treatment experiment row 1
As seen in the results of 2 and 2, the compound of the present invention showed excellent herbicidal efficacy against annual and perennial major weeds in paddy fields in both pre- and post-emergence treatments and during the growing season. Moreover, it was found to be highly safe for paddy rice.

次に畑地での実験例を示す。Next, we will show an example of an experiment conducted in a field.

実験例３ 直径８ｃｍｖさ８鍋の円型プラスチックケースに畑土壌
の一定量をつめ、メヒシバ、エノコログサ、イヌビニ、
ンロザの種子を一定量播種して０５〜１Ｃｒｎ程度の覆
土をした。たＶちに本発明有効成分化合物な含有する製
剤をアール当り有効成分で１２．５〜２５０１となるよ
うに調整した希釈液を土壌表面全面に処理した。処理後
は温室内で生育管理し２０日目に除草効果を調査した。Experimental Example 3 A certain amount of field soil was packed into a circular plastic case with a diameter of 8 cm and 8 pots.
A certain amount of N. rosa seeds were sown and covered with soil of about 0.05 to 1 Crn. Immediately thereafter, a diluted solution containing the active ingredient compound of the present invention was prepared to have an active ingredient content of 12.5 to 2,501 parts per area and was applied to the entire surface of the soil. After treatment, growth was controlled in a greenhouse, and the herbicidal effect was investigated on the 20th day.

実験は２連制で実施し、各々の平均値を求めた。なお調
査糸鋸は実験例１および２に同じであり、第４表の結果
を得た。The experiment was conducted in duplicate, and the average value of each was determined. Note that the investigation jig saw was the same as in Experimental Examples 1 and 2, and the results shown in Table 4 were obtained.

第４表　実験例３　雑草発芽前土壌処理実験例４゜ 直径８Ｃｒｎ深さ８Ｃｍの円型プラスチックケースに畑
土壌の一定量をつめ、エノコログサ、イヌビニの種子一
定量をそれぞれ播種して生育させ３〜４葉期に生育した
時に本発明有効成分化合物を含有する水和剤をアール当
り有効成分で１２．５１−１２５７および５０￥になる
ように希釈した液を植物体に散布した。Table 4 Experimental Example 3 Weed Pre-Germination Soil Treatment Experimental Example 4 A certain amount of field soil was packed into a circular plastic case with a diameter of 8 Crn and a depth of 8 Cm, and certain amounts of wild foxtail and dogfish seeds were sown and allowed to grow. When the plants had grown to the four-leaf stage, a solution prepared by diluting a hydrating powder containing the active ingredient compound of the present invention with the active ingredient to 12.51-1257 yen per area and 50 yen per area was sprayed on the plants.

実験は２連制で実施した。薬剤処理後２０日巨匠実験例
１及び２と同じ調査基準で調査し第５表の結果を得た。The experiment was conducted in duplicate. 20 days after the chemical treatment, an investigation was conducted using the same investigation criteria as in Master Experiments 1 and 2, and the results shown in Table 5 were obtained.

第５表　実験例４　雑草生育期処理 ・　　実験例５゜ 縦２３ｃｍ、横４５ｃｍ、深さ１２．５Ｃｒｎのプラス
チックバットに畑土壌の一定量をつめ、ダイズ、ワタ、
トウモロコシ、コムギ、ヒマワリおよびイネの種子を一
定量播種し、３Ｃｒｎ程度の覆土をした。Table 5 Experimental Example 4 Weed Growth Season Treatment Experimental Example 5 A certain amount of field soil was filled into a plastic vat measuring 23 cm long, 45 cm wide, and 12.5 crn deep, and soybean, cotton, etc.
A certain amount of corn, wheat, sunflower, and rice seeds were sown, and the soil was covered with about 3 cr.

ただちに本発明有効成分化合物を有する製剤をアール当
り有効成分で２５〜５０１となるように調整した希釈液
を各バット当９２０　ｍｌを小型噴霧器を使用し土壌表
面に処理した。処理後は温室内で生育管理し、２０日目
処各作物に対する薬害程度を調査した。実験は２連制で
実施し、各々の平均値を求めた。Immediately, 920 ml of a diluted solution of the preparation containing the active ingredient compound of the present invention adjusted to 25 to 501 active ingredients per area was applied to the soil surface using a small sprayer for each vat. After treatment, growth was controlled in a greenhouse, and the degree of chemical damage to each crop was investigated after 20 days. The experiment was conducted in duplicate, and the average value of each was determined.

なお調査基準は実験例１および２に同じであり第６表の
結果を得た。The investigation criteria were the same as in Experimental Examples 1 and 2, and the results shown in Table 6 were obtained.

第６表　実験例６ 実験例３および４の結果から明らかなように本発明化合
物は畑地の主要雑草に対して発芽前処理、生育処理で極
めてずぐれた除草効果を呈するものであることが判る。Table 6 Experimental Example 6 As is clear from the results of Experimental Examples 3 and 4, it can be seen that the compound of the present invention exhibits an extremely excellent herbicidal effect on major weeds in upland fields through pre-emergence treatment and growth treatment. .

捷だ実験例５の結果から明らかなように作物に対して薬
害がなく畑地用の除草剤としても好適なものである。As is clear from the results of Experimental Example 5, it is not harmful to crops and is suitable as a herbicide for upland fields.

特許出ム人　日本化薬株式会社Patent creator Nippon Kayaku Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] （１）式 （式中、Ｒ，は水素原子またはハロゲン原子を、■ｔ２
はハロゲン原子を、丁Ｌ３は水素原子または低級アルコ
キシ基によって置換されていてもよいＣ１〜Ｃ８の直鎖
または枝分れのアルキル基を、Ｘは酸素原子捷たはイオ
ウ原子を表わし、ｎは３又は４の整数を表わす） で示されるヒダントイン誘導体。 （式中、Ｒ１は水素原芋捷たは・・ロゲン原子を、Ｒ２
はハロゲン原子を、Ｒ３は水素原子または低級アルコキ
シ基によって置換されていてもよいＣ１〜Ｃ８の直鎖ま
たは枝分れのアルキル基を、Ｘは酸素原子またはイオウ
原子を表わし、【１は３又は４の整数を表わす） で示されるヒダントイン誘導体を有効成分とする除草剤
。(1) Formula (wherein, R is a hydrogen atom or a halogen atom, ■t2
represents a halogen atom, D3 represents a hydrogen atom or a C1 to C8 straight chain or branched alkyl group which may be substituted with a lower alkoxy group, X represents an oxygen atom or a sulfur atom, and n represents (representing an integer of 3 or 4) A hydantoin derivative represented by: (In the formula, R1 is a hydrogen atom or a rogen atom, R2
represents a halogen atom, R3 represents a hydrogen atom or a C1-C8 linear or branched alkyl group optionally substituted with a lower alkoxy group, X represents an oxygen atom or a sulfur atom, [1 is 3 or A herbicide containing a hydantoin derivative as an active ingredient (representing an integer of 4).
JP57158228A 1982-09-13 1982-09-13 Hydantoin derivative and herbicide containing said derivative as active component Pending JPS5948481A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
JP57158228A JPS5948481A (en) 1982-09-13 1982-09-13 Hydantoin derivative and herbicide containing said derivative as active component
ZA836359A ZA836359B (en) 1982-09-13 1983-08-26 A heterocyclic compound and a herbicidal composition containing said compound
AU18506/83A AU563282B2 (en) 1982-09-13 1983-08-29 Pyrrolidino and piperidino derivatives and condensed derivatives thereof
US06/527,493 US4531964A (en) 1982-09-13 1983-08-29 Heterocyclic compound and a herbicidal composition containing said compound
IL69615A IL69615A (en) 1982-09-13 1983-08-31 Derivatives of hydantoino(alkyleneiminocarbonyl amino)benzoic acid,process for their preparation and herbicidal compositions containing them
CA000436085A CA1210766A (en) 1982-09-13 1983-09-06 1-(n-heterocyclic containing)-3-carboxy-4-halogen- phenyl derivatives
DK407283A DK407283A (en) 1982-09-13 1983-09-08 HETEROCYCLIC COMPOUND AND A HERBICID AGENT CONTAINING THIS COMPOUND
HU833173A HU192160B (en) 1982-09-13 1983-09-12 Herbicide compositions containing hidantoine, thiohidantoine, pyrrolidine or piperidine derivatives as active agents, and process for producing the active agents
KR1019830004272A KR840006242A (en) 1982-09-13 1983-09-12 Method for preparing heterocycle compound
BR8304926A BR8304926A (en) 1982-09-13 1983-09-12 HERBICIDE COMPOUND, HERBICIDE COMPOSITION, PROCESS FOR KILLING WEEDS AND PROCESS TO PRODUCE A COMPOUND
EP83108992A EP0104532B1 (en) 1982-09-13 1983-09-12 O-halobenzoic acid derivatives, process for their preparation, herbicidal compositions and their use
AT83108992T ATE24004T1 (en) 1982-09-13 1983-09-12 O-HALOGENOBENZOIC ACID DERIVATIVES, PROCESS FOR THEIR PRODUCTION, HERBICIDE COMPOSITIONS AND THEIR USE.
DE8383108992T DE3368060D1 (en) 1982-09-13 1983-09-12 O-halobenzoic acid derivatives, process for their preparation, herbicidal compositions and their use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57158228A JPS5948481A (en) 1982-09-13 1982-09-13 Hydantoin derivative and herbicide containing said derivative as active component

Publications (1)

Publication Number Publication Date
JPS5948481A true JPS5948481A (en) 1984-03-19

Family

ID=15667073

Family Applications (1)

Application Number Title Priority Date Filing Date
JP57158228A Pending JPS5948481A (en) 1982-09-13 1982-09-13 Hydantoin derivative and herbicide containing said derivative as active component

Country Status (3)

Country Link
JP (1) JPS5948481A (en)
KR (1) KR840006242A (en)
ZA (1) ZA836359B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514341A1 (en) * 1991-05-17 1992-11-19 Sandoz Ltd. Novel heterocylic anilides for weed control

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514341A1 (en) * 1991-05-17 1992-11-19 Sandoz Ltd. Novel heterocylic anilides for weed control
US5312799A (en) * 1991-05-17 1994-05-17 Sandoz Ltd. Amides

Also Published As

Publication number Publication date
ZA836359B (en) 1984-04-25
KR840006242A (en) 1984-11-22

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