KR0140020B1 - Herbicidal sulfonamide derivatives - Google Patents
Herbicidal sulfonamide derivativesInfo
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- KR0140020B1 KR0140020B1 KR1019940027152A KR19940027152A KR0140020B1 KR 0140020 B1 KR0140020 B1 KR 0140020B1 KR 1019940027152 A KR1019940027152 A KR 1019940027152A KR 19940027152 A KR19940027152 A KR 19940027152A KR 0140020 B1 KR0140020 B1 KR 0140020B1
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- general formula
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
본 발명은 제초성 술폰아미드 유도체 화합물에 관한 것으로서, 더욱 상세하게는 벼농업에 있어서 발아전 및/또는 발아후 처리 제초제로서 유용한 에리스로 입체이성체를 갖는 다음 일반식(Ⅰ)로 표시되는 술폰아미드 유도체 화합물과 이를 사용하는 새로운 방법 및 이들 화합물을 포함하는 농업적으로 적절한 조성물에 관한 것이다.The present invention relates to herbicidal sulfonamide derivative compounds, and more particularly to sulfonamide derivative compounds represented by the following general formula (I) having erythro stereoisomers useful as pre- and / or post-germination treatment herbicides in rice farming. And new methods of using the same and agriculturally suitable compositions comprising these compounds.
여기서, Q는 서로 같거나 다른 것으로서 각각 CH 또는 N을 나타내고, P와 Q를 포함하는 아로마틱환은 벤젠 또는 피리딘환을 나타내며; R1은 H 또는기를 나타내며, 여기서 Ra는 C1~C3의 알킬기, C1~C3의 할로알킬기, C2~C3의 알케닐기, C2~C3의 알키닐기이고, Xa는 O, S, NH 또는 NRa기를 나타내고; R2는 C1~C2의알킬기이고; X와 Y는 각각 C1~C2의 알킬기, C1~C2의 알콕시기, C1~C2의 할로알콕시기 또는 할로겐을 나타낸다.Wherein Q is the same as or different from each other and represents CH or N, and the aromatic ring containing P and Q represents a benzene or pyridine ring; R 1 is H or Group represents where R a is an alkynyl group of C 1 ~ C 3 alkyl group, C 1 ~ C 3 in a haloalkyl group, C 2 ~ C 3 alkenyl group, C 2 ~ C 3 of a, X a is O, S, NH or NR a group; R 2 is a C 1 to C 2 alkyl group; X and Y each represent a C 1 to C 2 alkyl group, C 1 to C 2 alkoxy group, C 1 to C 2 haloalkoxy group or halogen.
Description
본 발명은 제초성 술폰아미드 유도체 화합물에 관한 것으로서, 더욱 상세하게는 벼농업에 있어서 발아전 및/또는 발아후 처리 제초제로서 유용한 에리스로 입체이상체를 갖는 다음 일반식(Ⅰ)로 표시되는 술폰아미드 유도체 화합물과 이를 사용하는 새로운 방법 및 이들 화합물을 포함하는 농업적으로 적절한 조성물에 관한 것이다.The present invention relates to herbicidal sulfonamide derivative compounds, and more particularly to sulfonamide derivative compounds represented by the following general formula (I) having erythro stereoisomers useful as pre- and / or post-germination treatment herbicides in rice farming. And new methods of using the same and agriculturally suitable compositions comprising these compounds.
여기서, P와 Q는 서로 같거나 다른 것으로서 각각 CH 또는 N을 나타내고; R1은 H 또는기를 나타내며, 여기서 Ra는 C1~C3의 알킬기, C1~C3의 할로알킬기, C2~C3의 알케닐기, C2~C3의 알키닐기이고, Xa는 O, S, NH 또는 NRa기를 나타내고; R2는 C1~C2의 알킬기이고; X와 Y는 각각 C1~C2의 알킬기, C1~C2의 알콕시기, C1~C2의 할로알콕시기 또는 할로겐을 나타낸다.Wherein P and Q are the same as or different from each other and represent CH or N, respectively; R 1 is H or Group represents where R a is an alkynyl group of C 1 ~ C 3 alkyl group, C 1 ~ C 3 in a haloalkyl group, C 2 ~ C 3 alkenyl group, C 2 ~ C 3 of a, X a is O, S, NH or NR a group; R 2 is an alkyl group of C 1 to C 2 ; X and Y each represent a C 1 to C 2 alkyl group, C 1 to C 2 alkoxy group, C 1 to C 2 haloalkoxy group or halogen.
종래에도 제초활성을 갖는 술포닐우레아 유도체 화합물이 다수 알려져 있었는바, 예를 들면 대한민국 특허출원공고 제 93-9825호에는 다음 일반식(A)와 같은 화합물이 알려져 있다.Conventionally, many sulfonylurea derivative compounds having herbicidal activity have been known. For example, Korean Patent Application Publication No. 93-9825 discloses a compound represented by the following general formula (A).
여기서, R은 할로알킬기이고, X 와 Y는 각각 CH3, OCH3, 또는 Cl 등이고, Z는 CH 또는 N이다.Wherein R is a haloalkyl group, X and Y are each CH 3 , OCH 3 , or Cl, and Z is CH or N.
또한, 대한민국 특허출원공고 제 93-9507호에는 다음 일반식(B)와 같은 제초성 피리딘술폰아미드 화합물이 알려져 있다.In addition, Korean Patent Application Publication No. 93-9507 discloses a herbicidal pyridine sulfonamide compound represented by the following general formula (B).
여기서, R, X, Y 및 Z는 위에서 기술한 바와같고, P와 Q는 N 또는 CH로서 피리딘환을 나타낸다.Here, R, X, Y and Z are as described above, and P and Q represent a pyridine ring as N or CH.
그러나, 이들 화합물들에 있어서, R기가 비대칭 탄소를 포함하는 경우에는 전체적으로 두개의 비대칭 탄소가 존재하게 되어 에리스로(Erythro-) 또는 스레오(Thero-) 입체이성체가 존재하게 되는데, 이들 입체이성체 중 어느 이성체는 혼합물 또는 다른 이성체 보다 월등히 높은 선택성과 활성을 나타내는 경우도 있다.However, in these compounds, when the R group contains an asymmetric carbon, two asymmetric carbons exist as a whole, resulting in the presence of an Erythro- or Thero- stereoisomer, which of these stereoisomers Isomers sometimes exhibit significantly higher selectivity and activity than mixtures or other isomers.
따라서, 본 발명은 이와 같이 새로운 구조를 갖고 있는 입체 이성체 중 어느 한쪽의 이성체를 새로이 규명해 냄으로서, 이들 신규화합물들이 제초활성이 매우 탁월할 뿐만 아니라 벼에 대하여 우수한 선택성을 나타내고 있는 이성체 화합물에 관한 것이다.Accordingly, the present invention newly identifies an isomer of any one of stereoisomers having such a new structure, and relates to an isomer compound in which these novel compounds not only have excellent herbicidal activity but also show excellent selectivity to rice. will be.
즉, 수도 농업에서 문제가 되고 있는 일년생 및 다년생 잡초 뿐만 아니라 기존 술포닐우레아 제초제로는 방제가 어려워 특히 문제가 되는 피를 탁월하게 방제함과 아울러 그 선택성 폭도 충분하여 수도용 제초제로서 매우 유용한 새로운 술폰아미드 유도체 화합물을 제공하는데 그 목적이 있다.That is, new sulfonamides, which are very useful as water herbicides because they are difficult to control with existing sulfonyl urea herbicides as well as annual and perennial weeds that are a problem in capital agriculture, and have a wide range of selectivity. It is an object to provide derivative compounds.
이하, 본 발명은 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 다음 일반식(Ⅰ)과 같은 구조의 신규한 에리스로 입체이성체를 치환체로 갖는 술폰아미드 화합무로서 벼에 대하여 선택성을 나타내는 재초성화합물 및 그들의 농업적으로 적당한 염에 관한 것이다.The present invention relates to a sulfonamide compound having a novel erythrostereoisomer having a structure as shown in the following general formula (I) as a substituent, and a herbicidal compound exhibiting selectivity to rice and agriculturally suitable salts thereof.
여기서, P, Q, R1, R2, X 및 Y는 상기 일반식(Ⅰ)에서 정의한 바와 같다.Here, P, Q, R 1 , R 2 , X and Y are as defined in the general formula (I).
상기 일반식(Ⅰ)로 표시되는 본 발명의 에리스로 화합물 중에서 벼에 대하여 선택성이 좋고 활성이 높은 화합물로서 더욱 바람직한 것은, (1) P와 Q가 각각 CH인 벤젠 화합물 (2) P가 N이고, Q가 CH인 피리딘 화합물 (3) R1이 H 또는 아세틸기인 화합물 (4) R2가 CH3인 화합물 (5) X와 Y가 메톡시인 화합물의 경우이다.Among the erythro compounds of the present invention represented by the above general formula (I), those compounds having a high selectivity and high activity with respect to rice are more preferably (1) a benzene compound in which P and Q are CH (2) P is N, Pyridine compound in which Q is CH (3) Compound in which R 1 is H or an acetyl group (4) Compound in which R 2 is CH 3 (5) In the case of a compound in which X and Y are methoxy.
이들 중에서 특히 벼농사에 문제가 되는 다년생 잡초 이외에도 피를 잘 방제함으로서 수도용제초제 성분으로서 농업적으로 적절하게 조제하여 사용하기에 좋고, 특히 벼에 대하여 선택성이 높은 화합물을 구체적으로 예시하면; 에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-[(4,6-디메톡시-피리미딘-2-일)아미노카보닐]-3-피리딘술폰아미드(화합물 번호1), 에리스로-N-[4,6-디메톡시-피리미딘-2-일)아미노카보닐]-2-(2-플루오로-1-히드록시-n-부틸)-3-피리딘술폰아미드 (화합물 번호 2), 에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-[(4,6-디메톡시-피리미딘-2-일)아미노카보닐]벤젠술폰아미드 (화합물 번호 3), 에리스로-N-[(4,6-디메톡시-피리미딘-2-일)아미노카보닐]-2-(2-플루오로-1-히드록시-n-부틸)벤젠술폰아미드 (화합물 번호 4) 등을 들 수 있다.Among them, especially the perennial weeds, which are a problem in rice farming, it is good to control and use agriculturally as a water herbicide component by controlling blood well, and specifically, a compound having high selectivity to rice is specifically exemplified; Erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N-[(4,6-dimethoxy-pyrimidin-2-yl) aminocarbonyl] -3-pyridinesulfonamide (compound 1), erythro-N- [4,6-dimethoxy-pyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxy-n-butyl) -3-pyridinesulphone Amide (Compound No. 2), erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N-[(4,6-dimethoxy-pyrimidin-2-yl) aminocarbonyl] benzene Sulfonamide (Compound No. 3), erythro-N-[(4,6-dimethoxy-pyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxy-n-butyl) Benzenesulfonamide (compound number 4), and the like.
상기와 같은 본 발명에 따른 일반식(Ⅰ)의 에리스로 화합물들은 에리스로(Erythro)-스레오(Threo) 혼합물 또는 스레오(Threo) 화합물에 비하여 훨씬 강력한 제초활성을 나타낼 뿐만 아니라 벼에 대하여 선택성이 우수하여 수도용 제초제 조성물의 성분으로서 매우 유용한 것으로 나타났다.The erythro compounds of the general formula (I) according to the present invention as described above not only exhibit much stronger herbicidal activity than erythro-Threo mixtures or Threo compounds, but also have excellent selectivity to rice. It has been found to be very useful as a component of the water herbicide composition.
이러한 상기 일반식(Ⅰ)로 표시되는 순수 에리스로 화합물을 제조하는 방법을 설명하면 다음과 같은 바, 본 발명에서 예시하는 방법 이외의 합성법으로도 이들 화합물은 합성될 수 있다.When explaining a method for producing a pure erythroxy compound represented by the general formula (I) as described below, these compounds can be synthesized by a synthetic method other than the method exemplified in the present invention.
본 발명에 따른 상기 일반식(Ⅰ)의 화합물 중 R1이 H인 화합물은 R1이 아세틸과 같은 아실인 화합물을 알카리 존재하에서 가수분해 시킴으로써 제조할 수 있다.Compounds in which R 1 is H in the compound of Formula (I) according to the present invention may be prepared by hydrolyzing a compound in which R 1 is acyl such as acetyl in the presence of alkali.
여기서 적당한 알카리는 LiOH, KOH, NaOH, Li2CO3, Na2CO3, K2CO3등이 모두 가능하며 이중 더욱 좋기로는 LiOH이다.Suitable alkali here may be LiOH, KOH, NaOH, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 and the like, more preferably LiOH.
또한 가수분해 반응은 물 또는 유기용매 존재하에서나 혼합용매하에서 반응시키는데, 물 이외에 메탄올, 에탄올, 아세톤, 테트라히드로푸란, 디메틸포름아미드 등과 같이 반응에 관여하지 않는 용매중에서 선택하며, 이들은 단독 또는 이들의 혼합 또는 물과 혼합한 용매하에서 반응시킬 수 있으며, 반응온도는 0℃~80℃ 범위에서 1~24시간 이내에 반응시킬 수 있다.In addition, the hydrolysis reaction is carried out in the presence of water or an organic solvent or in a mixed solvent, in addition to water, it is selected from solvents not involved in the reaction, such as methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide, etc. The mixture may be reacted in a solvent mixed or mixed with water, and the reaction temperature may be reacted within 1 to 24 hours in the range of 0 ° C to 80 ° C.
이렇게 제조된 생성물, 즉 상기 일반식(Ⅰ) 화합물의 분리는 염산수용액으로 산성화하면 쉽게 유리되며, 다른 방법으로는 산성화한 후 메틸렌클로라이드, 에틸아세테이트 유기용매로 추출한 후 농축하면 원하는 생성물을 얻을 수 있다.The product thus prepared, that is, the separation of the compound of general formula (I) is easily liberated by acidification with an aqueous hydrochloric acid solution. Alternatively, the desired product can be obtained by acidification, extraction with methylene chloride, ethyl acetate organic solvent and concentration. .
또한, 필요한 경우 HPLC 등으로 정제하면 더욱 순수한 생성물을 얻을 수 있다. 이를 반응식으로 나타내면 아래와 같다.Also, if necessary, purification by HPLC or the like can provide a more pure product. This is represented by the following reaction scheme.
상기식들중에서, P, Q, R2, X 및 Y는 각각 상기 일반긱(Ⅰ)에서 정의한 바와 같고, R1은 상기 일반식(Ⅰ)에서 정의한 것중 H인 경우를 제외한다.In the above formulas, P, Q, R 2 , X and Y are as defined in the general formula (I), respectively, and R 1 is the case of H defined in the general formula (I).
또한 상기 본 발명에 따른 일반식(Ⅰ) 화합물은 아래의 반응식과 같이 에리스로 입체구조를 갖는 다음 일반식(Ⅱ)의 화합물을 다음 일반식(Ⅲ])의 화합물과 반응시켜 제조할 수 있다.In addition, the compound of formula (I) according to the present invention can be prepared by reacting a compound of the following formula (II) having an erythro steric structure with the compound of the following formula (III) as shown in the following scheme.
상기식들중에서, P, Q, R1, R2, X 및 Y는 각각 상기 일반식(Ⅰ)에서 정의한 바와 같다.In the above formulas, P, Q, R 1 , R 2 , X and Y are as defined in the general formula (I), respectively.
상기 반응에서는 본 반응과 무관한 용매, 예를들자면 테트라히드로푸란, 아세톤, 아세토니트릴, 디옥산, 메틸렌클로라이드, 톨루엔, 부타논, 피리딘, 디메틸포름아미드 등이 사용될 수 있다.In the reaction, a solvent unrelated to the present reaction, for example, tetrahydrofuran, acetone, acetonitrile, dioxane, methylene chloride, toluene, butanone, pyridine, dimethylformamide, and the like may be used.
또한 소량의 감염기, 즉 DBU 또는 DABCO 등이 함께 사용되는 것이 좋으며 반응온도는 20~80℃ 범위로 유지하는 것이 좋다.In addition, a small amount of infecting device, that is, DBU or DABCO is preferably used together and the reaction temperature is good to maintain in the range of 20 ~ 80 ℃.
이 반응은 미국특허 제 4,445,245호에 기재되어 있는 방법으로서, 그 반응 후에는 유럽특허 제 44,8,7호에 기재되어 있는 바와 같이 산으로 처리하여 원하는 생성물을 얻을 수 있다.This reaction is a method described in US Pat. No. 4,445,245, after which the reaction can be treated with an acid to obtain the desired product, as described in EP 44,8,7.
또한 더욱 순도높은 생성물을 얻고자 할때는 컬럼 크로마토그래피(columnchromatography)로 정제하면 좋다.In addition, if you want to obtain a higher purity product may be purified by column chromatography (columnchromatography).
여기서, DBU는 1,8-디아자바이싸이클로[5.4.0]운데센-7-엔이고, DABCO는 1,4-디아자바이싸이클로[2.2.2]옥탄을 나타내며, 이하의 설명에서도 동일하다.Here, DBU is 1,8- diazabicyclo [5.4.0] undecene-7-ene, DABCO shows 1, 4- diazabicyclo [2.2.2] octane, and the same is also demonstrated below.
상기 일반식(Ⅲ) 화합물은 기존에 알려진 물질로서 기존의 방법에 따라 쉽게 제조할 수 있다.The general formula (III) compound is a known substance and can be easily prepared according to conventional methods.
또한 본 발명에서 상기 일반식(Ⅱ)의 에리스로 화합물은 다음 반응물과 같이 제조될 수 있다.In addition, in the present invention, the erythro compound of Formula (II) may be prepared as the following reactant.
상기식들중에서, P, Q, R1및 R2는 각각 상기에서 정의한 바와 같다.In the above formulas, P, Q, R 1 and R 2 are each as defined above.
상기 반응에서 TFA는 트리플루오로아세트산으로서, 상기 일반식(Ⅳ)의 화합물을 TFA를 용매로 하여 0~50℃의 온도하에서 교반하면 N-t-부틸기가 이탈하여 상기 일반식(Ⅱ)의 1급 술폰아미드의 에리스로 화합물이 얻어진다.In the reaction, TFA is trifluoroacetic acid. When the compound of Formula (IV) is stirred at a temperature of 0 to 50 ° C. using TFA as a solvent, Nt-butyl group is released and the primary sulfone of Formula (II) The erythro compound of the amide is obtained.
또한 상기 일반식(Ⅳ)화합물은 에리스로-스레오 혼합물을 컬럼크로마토그래피, HPLC 또는 prep-TLC 방법 등으로 분리하여 순수한 에리스로 화합물을 얻을 수 있다.In addition, the compound of formula (IV) can be obtained by separating the erythro-sreo mixture by column chromatography, HPLC or prep-TLC method, etc., to obtain a pure erythro compound.
또한 상기 일반식(Ⅳ) 화합물은 아래 일반식(Ⅴ)의 화합물을 통상의 방법으로 아실화하여 얻을 수 있다.In addition, the said general formula (IV) compound can be obtained by acylating the compound of the following general formula (V) by a conventional method.
다음 일반식(Ⅴ) 화합물은 아래의 반응식과 같이 다음 일반식(Ⅵ)의 화합물을 예컨대 DIBAL·H와 같은 적절한 선택 환원제를 이용하여 선택적으로 환원시킴으로써 얻을 수 있다.The following general formula (V) compound can be obtained by selectively reducing the compound of the following general formula (VI) with an appropriate selective reducing agent such as, for example, DIBAL.H, as shown in the following scheme.
상기식들중에서, P, Q 및 R2는 각각 상기에서 정의한 바와 같고, DIBAL·H는 디이소부틸알루미늄 하이드라이드(Diisobutylaluminum hydride)를 의미한다.In the above formulas, P, Q and R 2 are each as defined above, and DIBAL.H means Diisobutylaluminum hydride.
상기 반응에 있어서, P가 N이고 Q가 CH일때가 더욱 좋다.In the above reaction, it is better when P is N and Q is CH.
순도 높은 에리스로 이성체를 얻고자 할때는 크로마토그래피법으로 정제하면 쉽게 얻을 수 있다.When the isomer is to be obtained with high purity erythase, it can be easily obtained by purification by chromatography.
또한 본 발명에서 사용된 상기 일반식(Ⅳ)의 화합물은 다음의 반응식과 같은 방법으로 제조할 수 있다.In addition, the compound of Formula (IV) used in the present invention can be prepared by the same method as the following scheme.
상기식들중에서, P, Q 및 R2는 상기 일반식(Ⅰ)에서 정의한 바와 같고, R1은 상기 일반식(Ⅰ)에서 정의한 것중 H인 경우를 제외하고, L은 알콕시, N(CH3)2, 또는 NCH3(OCH3) 등을 나타낸다.In the above formulas, P, Q and R 2 are as defined in the general formula (I), and R 1 is alkoxy, N (CH 3) , except that H is defined in the general formula (I). ) 2 , or NCH 3 (OCH 3 ) and the like.
상기 반응식은 대한민국 특허출원공고 제 93-9825호, 동 제 93-9507호에 이미 알려져 있는 바, 일반식(Ⅶ)의 t-부틸술폰아미드에 2당량의 n-부틸리튬을 THF 용액에서 -100~+30℃의 온도로 1~2시간 처리하면 디리티오(dilithio) 염이 생성되며, 이 염을 -100~40℃의 온도로 유지하면서를 가해주면 케톤화합물이 생성되고, 이 케톤화합물을 NaBH4로 환원하고 생성된 히드록시화합물을 무수 초산/DMAP/피리딘 반응조건에서 아실화하여 R1이 아세틸인 일반식(Ⅷ)의 화합물을 얻는다.The reaction scheme is already known in Korean Patent Application Publication Nos. 93-9825 and 93-9507. Two equivalents of n-butyllithium in t-butylsulfonamide of the general formula Treatment with a temperature of ˜ + 30 ° C. for 1 to 2 hours produces dilithio salts, while maintaining the salt at a temperature of −100 to 40 ° C. Is added to form a ketone compound, the ketone compound is reduced to NaBH 4 and the resulting hydroxy compound is acylated under acetic anhydride / DMAP / pyridine reaction to give a compound of the general formula wherein R 1 is acetyl. .
상기 일반식(Ⅷ)의 화합물로부터 상기 일반식(Ⅳ)의 화합물을 얻는 방법은 HPLC, 컬럼크로마토그래피, 또는 prep-TLC방법 등으로 분리 정제하면 쉽게 상기 일반식(Ⅳ)의 에리스로 화합물을 얻을 수 있다.The method of obtaining the compound of the general formula (IV) from the compound of the general formula (VII) can be easily obtained by separating and purifying by HPLC, column chromatography, or prep-TLC method. have.
상기와 같이 제조되는 본 발명의 일반식(Ⅰ) 화합물들은 적절한 염의 형태로서도 제초제로서 유용하며 기존의 기술을 이용하여 여러가지 방법으로 제조할 수 있다. 예를들면 수산기, 알콕시드 또는 카보네이트를 가진 알카리나 알카리토금속 염기의 용액과 상기의 일반식(Ⅰ)의 화합물들을 접촉시킴으로써 적절한 염을 만들 수 있고 아민화합물들도 유사한 방법으로 염을 만들 수 있다.Formula (I) compounds of the present invention prepared as described above are also useful as herbicides in the form of suitable salts and can be prepared by various methods using existing techniques. For example, a suitable salt can be made by contacting a solution of an alkali or alkaline earth metal base with a hydroxyl group, alkoxide or carbonate with the compounds of the general formula (I) above, and amine compounds can be prepared in a similar manner.
또한, 상기 일반식(Ⅰ) 화합물들의 염을 한가지 양이온을 다른 것으로 교환함으로써 얻을 수 있다.It is also possible to obtain salts of the above general formula (I) compounds by exchanging one cation for another.
양이온 교환은 일반식(Ⅰ) 화합물의 한가지 염의 수용액, 예를들자면 알카리금속 또는 4급아민염 수용액을 교환시킬 양이온을 함유하는 용액과 직접적으로 접촉시킴으로써 만들 수 있다. 이 방법은 교환된 양이온을 함유하는 원하는 염이 물에 불용일때가 가장 효과적이다.Cation exchange can be made by directly contacting an aqueous solution of one salt of the general formula (I) compound, for example an aqueous alkali metal or quaternary amine salt solution, with a solution containing a cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water.
이러한 이온교환은 일반식(Ⅰ) 화합물의 염의 수용액, 예를들자면 알카리금속 또는 4급 아민염수용액을 교환될 양이온을 함유하는 양이온교환수지로 충진된 칼럼을 통과시킴으로서도 얻을 수 있다.Such ion exchange can also be obtained by passing an aqueous solution of a salt of the compound of formula (I), for example an alkali metal or quaternary amine salt solution, through a column filled with a cation exchange resin containing the cation to be exchanged.
이 방법에서는 수지의 양이온이 원래 염의 양이온과 교환되며 원하는 생성물은 칼럼으로부터 흘러나온다. 이 방법은 원하는 염이 수용성일때 즉, 소디움, 포타시움 또는 칼슘염일때가 특히 유용하다.In this method, the cation of the resin is exchanged with the cation of the original salt and the desired product flows out of the column. This method is particularly useful when the desired salt is water soluble, that is, sodium, potassium or calcium salts.
또한, 상기 일반식(Ⅰ) 화합물들은 우레아나 아미드화합물들과 혼합물 또는 착물을 이루어 제초제로서 유용하게 사용되며, 이러한 혼합물 또는 착물은 통상의 기술로 제조할 수 있다.In addition, the compounds of the general formula (I) are usefully used as herbicides by forming mixtures or complexes with urea or amide compounds, and such mixtures or complexes may be prepared by conventional techniques.
상기에 설명한 여러 제조방법에 관한 내용들은 간략하게 요약된 것들이지만 유기합성이나 술폰아미드 제초제의 합성분야에서 통상의 지식을 가진 사람이라면 쉽게 시행할 수 있는 내용들로서, 변형가능한 범위를 모두 포함한다.The contents of the various preparation methods described above are briefly summarized, but can be easily implemented by those skilled in the art of organic synthesis or synthesis of sulfonamide herbicides, and include all modifications.
이러한 본 발명의 방법에 의하여 얻어질 수 있는 일반식(Ⅰ)의 화합물들을 좀더 명확히 하기 위하여 개개의 화합물들로 예시하여 나타내면 다음 표 1에서 보는 바와 같다.In order to clarify the compounds of the general formula (I) that can be obtained by the method of the present invention as shown in the individual compounds as shown in Table 1 below.
상기와 같은 본 발명에 따른 일반식(Ⅰ)의 술폰아미드 유도체 에리스로 화합물은 제초제로서 유용한 바 적용방법에 관해 설명하면 다음과 같다.When the sulfonamide derivative erythro compound of the general formula (I) according to the present invention is useful as a herbicide, the application method is as follows.
[용도(utility)][Utility]
본 발명의 화합물들은 검정결과 발아전처리 또는 발아후처리 제초제로서 극히 고활성을 나타내며, 수도용 제초제로서는 수면처리 또는 경엽처리 제초제로서도 극히 고활성을 나타낸다.The compounds of the present invention show extremely high activity as a pre-germination or post-germination herbicide as a result of the assay, and extremely high activity as a sleeping or foliage treatment herbicide as a water herbicide.
본 발명의 활성화합물의 사용량은 여러가지 요인에 의해 결정되는데, 예를들자면 제어해야할 잡초에 따라 달라지고, 기후나 일기, 제형, 적용방법, 잡초의 크기 등에 따라 달라진다.The amount of active compound of the present invention is determined by various factors, for example, depending on the weeds to be controlled, and depends on the weather, weather, formulation, application method, weed size, and the like.
일반적으로 사용되는 활성성분의 양은 헥타아르(ha)당 1g에서 1㎏ 수준까지이며 저약량은 유기물 함량이 적은 토양이나 사질양토 등에 사용할 때이거나, 식물이 어릴때에 또는 약효의 단기간 지속이 요구될때에 사용한다.Generally, the amount of active ingredient used is from 1g to 1kg per hectare (ha), and the low dose is used for soil or sand loam with low organic content, when the plant is young or when the short-term duration of the medicinal effect is required. use.
본 발명의 화합물이 잡초방제에 특히 유효하게 사용될 수 있는 분야는 벼농사인데, 이들 농사에 발현하는 광엽잡초나 화본과잡초 또는 일년생 및 다년생 잡초의 방제에 매우 효과적이다. 특히피의 방제에 탁월한 효과를 나타낸다.The field in which the compound of the present invention can be used particularly effectively for weed control is rice farming, which is very effective for controlling broadleaf weeds, grass weeds, or annual and perennial weeds expressed in these farming fields. In particular, it shows an excellent effect on the control of blood.
한편, 본 발명의 화합물로 방제가 가능한 잡초들은 아래의 사용가능한 잡초리스트에 나타낸 바와 같다.On the other hand, weeds that can be controlled with the compound of the present invention are as shown in the following available weed list.
[사용가능한 잡초][Available weeds]
쌍떡잎식물 잡초속:Dicotyledonous weeds:
시나피스(Sinapis), 레피듐(Lepidium), 갈륨(Galium), 스텔라리아(Stellaria), 마트리카리아(Matricaria), 안테미스(Anthemis), 갈린소가(Galinsoga), 케노포듐(Chenopodium), 유르티카(Urtica), 세네시오(Senecio), 아마란투스(Amaranthus), 포르투라카(Portulaca), 크산튬(Xanthium), 콘볼불러스(Convolvulus), 이포모에아(Ipomoea), 폴리고늄(Polygonum), 세스바니아(Sesbania), 암브로시아(Ambrosia), 시르슘(Cirsium), 카르투스(Carduus), 손쿠스(Sonchus), 솔라눔(Solanum), 로리파(Rorippa), 로탈라(Rotala), 린데르니아(Lindernia), 라뮴(Lamium), 베로니카(Veronica), 아부틸론(Arbutilon), 에멕스(Emex), 다투라(Datura), 비올라(Viola), 갈레오프시스(Galeopsis), 파파베르(Papaver), 센타우레아(Centaurea).Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Kenopodium, Urtica, Senesio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Cardus, Sonchus, Solanum, Rorippa, Rotala, Lindernia Lindernia, Lamium, Veronica, Arbutilon, Emex, Datura, Viola, Galeopsis, Papaver, Center Urea (Centaurea).
외떡잎식물 잡초속:Monocotyledonous weeds:
에키노클로아(Echinochloa), 세타리아(Setaria), 파니쿰(Panicum), 디지타리아(Digitaria), 플레움(Phleum), 포아(Poa), 페스투카(Festuca), 엘레우신(Eleusine), 브라키아리아(Brachiaria), 롤륨(Lolium), 브로무스(Bromus), 아베나(Avena), 사이페러스(Cyperus), 소르검(Sorghum), 아그로피론(Agropyron), 시노돈(Cynodon), 모노코리아(Monochoria), 펌브리스틸리스(Fimbristylis), 사기타리아(Sagittaria), 엘레오카리스(Eleocharis), 스르푸스(Scirpus), 파스팔륨(Paspalum), 다크틸록테늄(Dactyloctenium), 아그로스티스(Agrostis), 알로페쿠러스(Alopecurus), 아페라(Apera), 헤테란테라(Heteranthera), 렙토클로아(Leptochloa).Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Mono Korea (Monochoria), Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Dactyloctenium, Agrostis , Alopecurus, Apera, Heteranthera, Leptochloa.
본 발명의 화합물들은 단독으로 사용될 수도 있고 기존에 알려진 약제들과 혼합되어 2원, 3원 또는 4원 합제 등으로 사용될 수도 있다.The compounds of the present invention may be used alone or in combination with known agents may be used in binary, tertiary or quaternary mixtures.
아래에 열거한 제품명의 리스트는 본 발명의 화합물들과 혼합물로서 사용하기에 적절한 제초제들이다.The list of product names listed below are herbicides suitable for use as a mixture with the compounds of the present invention.
본 발명 화합물과 아래 제초제중의 한개 또는 그 이상의 제초제들과 혼합하여 사용하는 것은 잡초제어에 특히 유용하다.The use of a mixture of the compound of the present invention with one or more of the following herbicides is particularly useful for weed control.
제품명(Common Name)Common Name
아세토클로르(acetochlor)아세플루오르펜(acifluorfen)Acetochlor acefluorfen
AC 252,214AC 263,499AC 252,214AC 263,499
아크롤레인(acrolein)알라클로로(alachlor)Acrolein alachlor
아메트린(ametryn)아미트롤(amitrole)Ametryn amitrol
AMS아술람(asulam)AMS asulam
아수레(assure)아트라진(atrazine)Assure Atrazine
BAS-514바반(barban)BAS-514 Barban
베네핀(benefin)벤술퍼론메틸(bensulfuron methyl)Benefin Bensulfuron Methyl
벤술라이드(bensulide)벤타존(bentazon)Bensulide Bentazon
벤조플루오르(benzofluor)벤조일프로프(benzoylprop)Benzofluor Benzoylprop
비페녹스(bifenox)브롬아실(bromacil)Bifenox bromacil
브롬옥시닐(bromoxynil)부타클로르(butachlor)Bromoxynil butachlor
부티다졸(buthidazole)부트랄린(butralin)Buthidazole butralin
부틸레이트(butylate)카코디릭애시트(cacodylic acid)Butylate Cacodylic Acid
CDAACDECCDAACDEC
CGA 82725CH-83CGA 82725CH-83
클로르암벤(chloramben)클로르브로뮤론(chlorbromuron)Chloramben chlorbromuron
클로리뮤론에틸(chlorimuron ethyl)클로르옥슈론(chloroxuron)Chlorimuron ethyl (chloroxuron)
클로르포르팜(chlorporpham)클로르술퍼론(chlorsulfuron)Chlorporpham chlorsulfuron
클로르톨루론(chlortoluron)신메티린(cinmethylin)Chlortoluron cinmethylin
클레토딤(clethodim)크로마존(clomazone)Clethodim clomazone
클로프록시딤(cloproxydim)클로피라리드(clopyralid)Cloproxydim clopyralid
CMA시아나진(cyanazine)CMA cyanazine
사이클로에이트(cycloate)사이클루론(cycluron)Cycloatecycluron
사이퍼쿼트(cyperquat)시아프라진(cyprazine)Cyperquat Cyprazine
사이프라졸(cyprazole)시프로미드(cypromid)Cyprazole cypromid
달라폰(dalapon)다조메트(dazomet)Dalapon dazomet
DCPA데스메디판(desmediphan)DCPAdesmediphan
데스메트린(desmetryn)디알레이트(diallate)Desmetryn dialalate
디캄바(dicamba)디클로르베닐(dichlorbenil)Dicamba dichlorbenil
디클로르프로프(dichlorprop)디클로포프(dichlofop)Dichlorprop dichlorofop
디에타틸(diethatyl)디펜조쿼트(difenzoquat)Diethatyl diffifquaquat
디니트라민(dinitramine)디노셉(dinoseb)Dinitramine dinoseb
디페나미드(diphenamid)디프로페트린(dipropetryn)Diphenamid dipropetryn
디쿼트(diquat)디우론(diuron)Diquat diuron
DNOCDOWCO 453 MEDNOCDOWCO 453 ME
DPX-M6316DSMADPX-M6316DSMA
엔도탈(endothall)EPTCEndothall EPTC
엔탈플루라린(ethalfluralin)에토푸메세이트(ethofumesate)Etalfluralin etofumesate
엑스프레스(express)페낙(fenac)Express fenac
페녹사프로프에틸(fenoxapropethyl)페누론(fenuron)Phenoxapropethyl fenuron
페누론(fenuron) TCA플람프로프(flamprop)Fenuron TCA flamprop
플루아지포프(fluazifop)플루아지포프부틸(fluazifopbutyl)Fluazifop fluazifopbutyl
플루아지포프(fluazifop)-P플루클로라린(fluchloralin)Fluazifop-P Fluchloralin
플루오메투론(fluometuron)플루오로클로리돈(fluorochloridone)Fluometuron Fluorochloridone
플루오로디펜(fluorodifen)플루오로글라이코펜(fluoroglycofen)Fluorodifen Fluoroglycofen
플루리돈(fluridone)포메사펜(fomesafen)Fluridone pomesafen
포사민(fosamine)글리포세이트(glyphosate)Fosamine glyphosate
할록시포프(haloxyfop)하르모네이(harmoney)Haroxyfop harmoney
헥사플루레이트(hexaflurate)헥사지논(hexazinone)Hexaflurate hexazinone
HW-52이마자메타벤즈(imazamethabenz)HW-52 imazamethabenz (imazamethabenz)
이마자피르(imazapyr)이마자퀸(imazaquin)Imazapyr imazaquin
이마제타피르(imazethapyr)이옥시닐(ioxynil)Imazethapyr ioxynil
이소프로팔린(isopropalin)이소프로투론(isoproturon)Isopropalin isoproturon
이소우론(isouron)이속사벤(isoxaben)Isouron isoxaben
카르부티레이트(karbutilate)락토펜(lactofen)Carbutilate lactofen
레나실(lenacil)리누론(linuron)Lenacil linuron
MAAMAMAMAAMAMA
MCPAMCPBMCPAMCPB
메코프로프(mecoprop)메플루이다이드(mefluidide)Mecoprop mefluidide
메탈프로파린(methalpropalin)메타벤즈티아주론(methabenzthiazuron)Metalpropalin metabenzthiazuron
메탐(metham)메타졸(methazole)Metham methazole
메톡수론(methoxuron)메톨라클로르(methazole)Methoxuron metolachlor (methazole)
메트리부진(metribuzin)메트술푸론메틸(metsulfuron methyl)Metribuzin metsulfuron methyl
MH몰리네이트(molinate)MH molinate
모노리누론(monolinuron)모누론(molinate)Monolinuron molinate
모노룬(monuron) TCAMSMAMonorun TCAMSMA
My-93나프로파미드(napropamide)My-93 napropamide
나프로아니리드(naproanilide)나프타람(naptalam)Naproanilide naptalam
네부론(neburon)니트탈린(nitralin)Neburon nitralin
니트로펜(nitrofen)니트로플루오르펜(nitrofluorfen)Nitrofen nitrofluorfen
노레아(norea)노르프루라존(norfrurazon)Norea norfrurazon
NTN- 801오리잘린(oryzalin)NTN-801Orizalin
옥사디아존(oxadiazon)옥시플루오르펜(oxyfluorfen)Oxadiazon Oxyfluorfen
파라쿼트(paraquat)페불레이트(pebulate)Paraquat pebulate
펜디메타린(pendimethalin)페르플루이돈(perfluidone)Pendimethalin (pendimethalin) perfluidone
펜메디팜(phenmedipham)피클로람(picloram)Phenmedipham picloram
PPG-1013프레틸아크로르(pretilachlor)PPG-1013 Pretilachlor
프로시아진(procyazine)프로플루랄린(profluralin)Procyazine and profluuralin
프로메톤(prometon)프로메트린(prometryn)Prometonprometryn
프로나미드(pronamide)프로파클로르(propachlor)Pronamide propachlor
프로파닐(propanil)프로파진(propazine)Propaneil propazine
프로팜(propham)프로술파린(prosulfalin)Propham prosulfalin
프리나클로르(prynachlor)피라존(pyrazon)Prynachlor pyrazon
파라졸레이트(pyrazolate)퀴잘로포프(quizalofop)Pyrazolatequizalofop
퀴잘로포프 에틸(quizalofop ethyl)SC-2957Quizalofop ethyl SC-2957
섹부메톤(secbumeton)세톡시딤(sethoxydim)Secbumeton sethoxydim
시두론(siduron)시마진(simazine)Siduron simazine
SL-49술포메투론 메틸(sulfometuron methyl)SL-49 sulfometuron methyl
TCA테부티우론(tebuthiuron)TCA tebuthiuron
테르바실(terbacil)테르부클로르(terbuchlor)Terbacil terbuchlor
테르부틸라진(terbuthylazine)테르부톨(terbutol)Terbuthylazineterbutol
테르부트린(terbutryn)티아메투론메틸(thiameturon methyl)Terbutryn thiameturon methyl
티오벤카브(thiobencarb)트리알레이트(triallate)Thiobencarb triallate
트리클로피르(triclopyr)트리디판(tridiphane)Triclopyr tridiphane
트리플루라린(trifluralin)트리메투론(trimeturon)Trifluralin trimeturon
2,4-D2,4-DB2,4-D2,4-DB
베르놀레이트(vernolate)X-52Vernolate X-52
크실라클로르(vernolate)사탄(Saturn)Xylachlor (Saturn)
KH-218NSK-850KH-218NSK-850
피라족시펜(Pyrazoxyfen)디멘존(Dimension)Pyrazoxyfen (Dimension)
CH-900메페나셀(Mefenacet)CH-900 Mefenacet (Mefenacet)
TSH-888디무론(Dymron)TSH-888 Dimuron
디메피페레이트(Dimepiperate)이속사피리포스(Isoxapyrifos)Dimepiperate isoxapyrifos
페노벤주론(Phenobenzuron)JC-940Phenobenzuron JC-940
에스프로캅(Esprocab)메틸벤캅(Methylbencab)Esprocab (Methylbencab)
페노필레이트(Phenopylate)벤퓨레세이트(Benfuresate)Phenopylate Benfuresate
S-275퀸클로락(Quinclorac)S-275Quinclorac
론닥스(Londax)NC-311Rondax (NC-311)
TH-913HW-52TH-913HW-52
DEH-112SKH-301DEH-112SKH-301
브로모부타이드(Bromobutide)BAS517HBromobutide BAS517H
RE45601RE36290RE45601RE36290
RO173664HOE075032RO173664HOE075032
ICIA6051DPXA7881ICIA6051DPXA7881
MW801CGA136872MW801CGA136872
DPXV9360DPXE9636DPXV9360DPXE9636
SL950ICIA02957SL950ICIA02957
CGAI42464MY15CGAI42464MY15
MON7200WL95481MON7200WL95481
DPXY6202MON15100DPXY6202MON15100
SL160ICIA0224SL160ICIA0224
LS83556BAS518HLS83556BAS518H
CGA131036DPXL5300CGA131036DPXL5300
HOE70542ICIA0604HOE70542ICIA0604
ICIA0574LS846215ICIA0574LS846215
[제제(Formulation)][Formulation]
본 발명의 일반식(Ⅰ) 화합물의 유용한 제제는 통상적인 여러방법으로 제조될 수 있는데 예를 들자면 분제, 입제, 펠렛, 용액, 현탁제, 유화제, 습윤성 분말제, 유화성 농축제 등이다.Useful formulations of the compounds of formula (I) of the present invention can be prepared by a variety of conventional methods, such as powders, granules, pellets, solutions, suspensions, emulsifiers, wettable powders, emulsifying thickeners and the like.
이들 중 몇가지 제제는 직접 사용할 수 있고, 스프레이용 제제는 헥타아르당 수 리터로부터 수백 리터까지 적절한 매체에 희석하여 분무할 수 있다.Some of these formulations can be used directly, and spray formulations can be sprayed by dilution in appropriate media from several liters to several hundred liters per hectare.
고강도 조제는 주로 2차 제제화를 위한 중간체로서 사용되기도 한다. 광의로서 제제는 활성성분을 중량비로써 0.1%부터 98.9%까지 함유하며 적어도 다음중 하나를 포함한다. 즉, (1) 약 0.1%부터 20%까지의 계면활성제 및 (2) 약 1%부터 99.8%까지의 고체 또는 액체 불활성 희석제를 함유한다.High strength preparations are often used as intermediates for secondary formulations. In broad terms, the formulation contains from 0.1% to 98.9% by weight of the active ingredient and comprises at least one of the following. That is, (1) from about 0.1% to 20% of surfactant and (2) from about 1% to 99.8% of a solid or liquid inert diluent.
더욱 구체적으로는 이들 성분은 다음 표 2와 같은 대략적인 비율로 구성된다.More specifically, these components are composed of the approximate ratio shown in Table 2 below.
*활성성분과 계면활성제 및 희석제를 합하여 중량비로 100%가 됨* Add up to 100% by weight of active ingredient, surfactant and diluent
활성성분의 함량도는 의도하는 용도에 따라서 또는 그 화합물의 물리적 성질에 따라서 높거나 낮을 수 있다.The content of active ingredient may be high or low depending on the intended use or the physical properties of the compound.
또한 활성성분에 대하여 계면활성제가 더 높은 비율로 필요할 때도 있는데, 이는 제제화 또는 탱크 혼합시 첨가함으로써 조절할 수 있다.There are also times when higher proportions of surfactant are required for the active ingredient, which can be controlled by addition during formulation or tank mixing.
대표적인 고체 희석제는 Watkins 등이 저술한 책인 Handbook of Insecticide Dust Diluents and Carriers 2nd Ed., Dorland Books, Caldwell, N. J., 에 기술되어 있으며, 다른 고체들도 사용될 수 있다.Representative solid diluents are described in Watkins et al. Handbook of Insecticide Dust Diluents and Carriers 2nd Ed., Dorland Books, Caldwell, N. J., other solids may be used.
흡수성이 더 높은 희석제가 습윤성 분말제로는 좋으며, 분제로써는 더 미세할수록 좋다.A higher absorbent diluent is good for the wettable powder, and the finer the powder, the better.
대표적 액체 희석제와 용제는 Marsden의 저서 Solvents Guide, 2nd Ed., Interscience, New York, 1950에 기술되어 있다. 용해도가 0.1% 이하인 것은 현탁농축제로서 좋으며, 용액 농축제는 0℃에서도 상분리가 일어나지 않고 안정한 것이 좋다.Representative liquid diluents and solvents are described in Marsden's book Solvents Guide, 2nd Ed., Interscience, New York, 1950. The solubility of 0.1% or less is good as a suspension thickener, and the solution thickener is stable without phase separation even at 0 ° C.
McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, N. J., 및 Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co., Inc., New York, 1964, 에는 계면활성제와 사용법에 대해서 기술하고 있다.McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, N. J., and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co., Inc., New York, 1964, describe surfactants and their use.
모든 제제들은 거품이나 뭉치는 것, 부식 및 미생물의 생장등을 방지하기 위하여 소량의 첨가제들이 함유될 수 있다. 이러한 여러가지 조성물을 만드는 방법들은 잘 알려져 있다.All formulations may contain small amounts of additives to prevent foaming or agglomeration, corrosion and microbial growth. Methods of making these various compositions are well known.
용액은 성분들을 단순히 섞기만 하면 만들 수 있고, 미세한 고체 조성물들은 혼합하여 만들고, 보통 분쇄하여 만는다. 현탁제제들은 wet milling 법(미국특허 제 3,060,084호 참조)으로 만들며 입제와 펠렛제는 미리 성형된 입제케리어에 활성 성분을 스프레이 하거나 또는 Agflomeration 법으로 만든다. J. E. Browning, Agglomeration Chemical Engineering, Dec. 4,1967, pp147와 Perry's Chemical Engineer's Handbook, 5th Ed., McGraw -Hill, New York, 1973, pp8-57ff를 참조하면 좋다.The solution can be made by simply mixing the components, and the fine solid compositions are mixed and usually ground. Suspensions are made by wet milling (see US Pat. No. 3,060,084) and granules and pellets are made by spraying the active ingredient on a preformed granular carrier or by agflomeration. J. E. Browning, Agglomeration Chemical Engineering, Dec. 4,1967, pp147 and Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York, 1973, pp8-57ff.
또한 제제 기술에 관해서는 다음 정보를 참고하면 좋다. US 3,235,361, US 3,309,192, US 2,891,855와 G.C. Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp.81-96 및 J. D. Fryer and S. A. Evans, Weed Control Handbook, 5th Ed., Blackwell Scientific Publications Oxford, 1968, pp. 101-103.In addition, the following information regarding formulation technology may be referred to. US 3,235,361, US 3,309,192, US 2,891,855 and G.C. Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp.81-96 and J. D. Fryer and S. A. Evans, Weed Control Handbook, 5th Ed., Blackwell Scientific Publications Oxford, 1968, pp. 101-103.
본 발명의 화합물들은 불필요한 잡초들을 제거하는데에 단독으로 사용될 수 있고 또는 기존의 다른 제초제들과의 합제로도 사용할 수 있다.The compounds of the present invention can be used alone to remove unwanted weeds or in combination with other existing herbicides.
본 발명에 의한 활성화합물들의 제조와 사용에 관하여 좀더 명확하게 하기 위하여 구체적 제조방법을 다음의 데표적 실시예로서 예시한다.Specific preparation methods are exemplified as the following target examples in order to clarify the preparation and use of the active compounds according to the present invention.
[실시예 1]Example 1
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-(1,1디메틸에틸)-3-피리딘술폰아미드 에리스로-N-1,1-디메틸에틸)-2-(2-플루오로-1-히드록시-n-부틸)-3-피리딘술폰아미드 1.0g 을 무수 염화메틸렌 20㎖에 녹인 후 정제된 무수아세트산 0.37g과 피리딘 0.29g 및 DMAP 50㎎을 넣고 실온에서 약 2시간 교반한다.Erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N- (1,1dimethylethyl) -3-pyridinesulfonamide erythro-N-1,1-dimethylethyl) -2- ( 1.0 g of 2-fluoro-1-hydroxy-n-butyl) -3-pyridinesulfonamide was dissolved in 20 ml of anhydrous methylene chloride, and 0.37 g of purified acetic anhydride, 0.29 g of pyridine and 50 mg of DMAP were added at about room temperature. Stir for 2 hours.
TLC 확인 후 30㎖의 물을 넣고 5% HCl로 약 산성화시킨 후 염화메틸렌으로 추출하고 다시 중수소나트륨 용액으로 씻고 소량의 물로 두번 씻어준 다음 무수 황산마그네슘으로 건조 후 감압 증발시켜 목적화합물 약 1.1g을 얻었다.After TLC check, add 30 ml of water, slightly acidify with 5% HCl, extract with methylene chloride, wash with sodium deuterium solution, wash twice with small amount of water, dry with anhydrous magnesium sulfate and evaporate under reduced pressure. Got it.
H NMR(200MHz, CDCl):δ H NMR (200 MHz, CDCl): δ
0.93(t,3H),1.3(s,9H),1.6~1.9(m,2H),2.8(s,3H),4.6~5.0(m,1H),0.93 (t, 3H), 1.3 (s, 9H), 1.6 ~ 1.9 (m, 2H), 2.8 (s, 3H), 4.6 ~ 5.0 (m, 1H),
5.6(bs,1H),6.54~6.61(dd,1H),7.3~7.4(m,1H),8.2~8.3(m,1H),5.6 (bs, 1H), 6.54 ~ 6.61 (dd, 1H), 7.3 ~ 7.4 (m, 1H), 8.2 ~ 8.3 (m, 1H),
8.65~8.75(m,1H).8.65-8.75 (m, 1 H).
[실시예 2]Example 2
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-3-피리딘술폰아미드 에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-(1,1-디메틸에틸)-3-피리딘술폰아미드 1.1g을 20㎖의 트리플루오로아세트산에 녹인 후 실온에서 하룻밤동안 교반한다.Erythro-2- (1-acetoxy-2-fluoro-n-butyl) -3-pyridinesulfonamide erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N- (1, 1.1 g of 1-dimethylethyl) -3-pyridinesulfonamide is dissolved in 20 ml of trifluoroacetic acid and stirred overnight at room temperature.
반응액을 감압하에서 농축하고 잔사를 염화메틸렌으로 녹인 후 중틴산나트륨 숭용액으로 씻어준다음 유기층을 무수 황산마그네슘으로 건조시키고 감압 증발시킨 후 에틸 아세테이트와 헥산으로 결정화하여 순수한 목적화합물 0.5g을 얻었다.The reaction solution was concentrated under reduced pressure, the residue was dissolved in methylene chloride, washed with sodium bicarbonate solution, and the organic layer was dried over anhydrous magnesium sulfate, evaporated under reduced pressure, and crystallized with ethyl acetate and hexane to obtain 0.5 g of a pure target compound.
H NMR(200MHz, CDCl):δ H NMR (200 MHz, CDCl): δ
1.06(t,3H),1.6~2.1(m,2H),2.13(s,3H),4.7~5.1(m,1H),1.06 (t, 3H), 1.6 ~ 2.1 (m, 2H), 2.13 (s, 3H), 4.7 ~ 5.1 (m, 1H),
5.65(br,1H),6.61(t,1H),7.4~7.5(m,1H),8.4~8.5(m,1H),5.65 (br, 1H), 6.61 (t, 1H), 7.4-7.5 (m, 1H), 8.4-8.5 (m, 1H),
8.8~8.9(m,1H).8.8-8.9 (m, 1H).
[실시예 3]Example 3
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-[(4,6-디메톡시피리미딘-2-일)아미노카보닐]-3-피리딘술폰아미드(화합물 번호1) 에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-3-피리딘술폰아미드 0.5g을 20㎖의 아세토니트릴에 녹인 후 0.5g의 페닐(4,6-디메톡시피리미딘-2-일)카바메이트를 실온에서 넣는다. 0.29g의 DBU를 서서히 넣으면서 반응액을 실온에서 교반시키고 약 2시간 후 TLC 확인하고 염화메틸렌 100㎖에 희석한다.Erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-pyridinesulfonamide (compound No. 1) 0.5 g of erythro-2- (1-acetoxy-2-fluoro-n-butyl) -3-pyridinesulfonamide was dissolved in 20 ml of acetonitrile and 0.5 g of phenyl (4,6-dimethock). Cipyrimidin-2-yl) carbamate is added at room temperature. While slowly adding 0.29 g of DBU, the reaction solution was stirred at room temperature. After about 2 hours, TLC was confirmed and diluted in 100 ml of methylene chloride.
50㎖의 물을 넣고 5% 염산수용액으로 약 산성화시킨 후 유기층을 분리하고 5㎖의 물로 두번 씻어준다.Add 50 ml of water, slightly acidify with 5% aqueous hydrochloric acid solution, separate the organic layer and wash twice with 5 ml of water.
유기층을 무수 황산나트륨으로 건조하고 감압 농축한 후 잔사에 에틸 에테르를 넣으면 고체화되며 목적화합물 0.6g을 백색 고체로 얻었다.The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and ethyl ether was added to the residue to solidify the residue, obtaining 0.6 g of the target compound as a white solid.
녹는점(℃): 184~186Melting Point (℃): 184 ~ 186
H NMR(200MHz, CDCl):δ H NMR (200 MHz, CDCl): δ
0.98(t,3H),1.6~2.0(m,2H),2.04(s,3H),3.99(s,6H),4.7~5.1(m,1H),0.98 (t, 3H), 1.6 ~ 2.0 (m, 2H), 2.04 (s, 3H), 3.99 (s, 6H), 4.7 ~ 5.1 (m, 1H),
5.8(s,1H),6.6~6.7(dd,1H),7.3(br,1H),745~7.55(m,1H),8.6~8.75.8 (s, 1H), 6.6 ~ 6.7 (dd, 1H), 7.3 (br, 1H), 745 ~ 7.55 (m, 1H), 8.6-8.7
(m,1H), 8.8~8.9(m,1H).(m, 1H), 8.8-8.9 (m, 1H).
[실시예 4]Example 4
에리스로-N-[4,6-디메톡시피리미딘-2-일]아미노카르보닐]-2-(2-플루오로-1-히드록시-n-부틸)-3-피리딘술폰아미드 (화합물 번호 2)Erythro-N- [4,6-dimethoxypyrimidin-2-yl] aminocarbonyl] -2- (2-fluoro-1-hydroxy-n-butyl) -3-pyridinesulfonamide (Compound No. 2)
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-[(4,6-디메톡시피리미딘-2-일)아미노카르보닐]-3-피리딘술폰아미드 0.3g을 메탄올 10㎖에 녹이고 수산화리튬 55㎎을 넣고 실온에서 4시간 교반시킨다.0.3 g of erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -3-pyridinesulfonamide Dissolve in 10 ml of methanol, add 55 mg of lithium hydroxide, and stir at room temperature for 4 hours.
교반 후 100㎖의 염화메틸렌으로 묽인 후 5% HCl로 약 산성화시킨 후 유기층을 5㎖의 물로 두번 씻어주고 무수 황산나트륨으로 건조 후 감압 농축한다.After stirring, the mixture was diluted with 100 ml of methylene chloride, slightly acidified with 5% HCl, the organic layer was washed twice with 5 ml of water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
잔사에 에틸 에테르를 넣으면 고체화되고 목적화합물 0.2g을 얻었다.Ethyl ether was added to the residue to solidify to obtain 0.2 g of the target compound.
녹는점(℃):129~130Melting Point (℃): 129 ~ 130
[실시예 5]Example 5
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-[(4,6-디메톡시피리미딘-2-일)아미노카보닐]벤젠술폰아미드 (화합물 번호 3)Erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] benzenesulfonamide (Compound No. 3)
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)벤젠술폰아미드 2g을 20㎖의 아세토니트릴에 녹이고 여기에 2g의 페닐-(4,6-디메톡시피리미딘-2-일)카바메이트를 실온에서 넣는다. 1㎖의 DBU를 서서히 주입하고 반응액을 30분동안 교반한 후 염화메틸렌 100㎖로 희석한다.2 g of erythro-2- (1-acetoxy-2-fluoro-n-butyl) benzenesulfonamide was dissolved in 20 ml of acetonitrile and 2 g of phenyl- (4,6-dimethoxypyrimidine-2- 1) Carbamate is added at room temperature. 1 ml of DBU is slowly injected and the reaction solution is stirred for 30 minutes and then diluted with 100 ml of methylene chloride.
5% 염산수용액 50㎖와 물 50㎖로 세척하고 유기층을 황산마그네슘으로 건조하고 여과하여 농축한다.Wash with 50 ml of 5% aqueous hydrochloric acid solution and 50 ml of water. The organic layer is dried over magnesium sulfate, filtered and concentrated.
여액을 에틸아세테이트/헥산/에틸 에테르로 처리하여 목적화합물 2.6g을 백색고체로 얻었다.The filtrate was treated with ethyl acetate / hexane / ethyl ether to give 2.6 g of the target compound as a white solid.
녹는점(℃):170~172Melting Point (℃): 170-172
H NMR(200MHz, CDCl):δ H NMR (200 MHz, CDCl): δ
0.94(t,3H,J=8Hz),1.54~1.80(m,2H),2.00(s,3H),3.99(s,6H),0.94 (t, 3H, J = 8 Hz), 1.54 to 1.80 (m, 2H), 2.00 (s, 3H), 3.99 (s, 6H),
4.66~4.93(m,1H),5.76(s,1H),6.74(dd,1H,J=14.8Hz,J=3Hz),4.66 ~ 4.93 (m, 1H), 5.76 (s, 1H), 6.74 (dd, 1H, J = 14.8Hz, J = 3Hz),
7.14(brs,1H),7.49~7.62(m,3H),8.34~8.35(m,1H), 13.06(brs,1H).7.14 (brs, 1 H), 7.49-7.62 (m, 3 H), 8.34-8.35 (m, 1 H), 13.06 (brs, 1 H).
IR(KBr)ν(C=O)1710,1755㎝ IR (KBr) ν (C = O) 1710,1755cm
[실시예 6]Example 6
에리스로-N-[(4,6-디메톡시피리미딘-2-일)아미노카보닐]-2-(2-플루오로-1-히드록시-n-부틸)벤젠술폰아미드 (화합물 번호 4)Erythro-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxy-n-butyl) benzenesulfonamide (Compound No. 4)
에리스로-2-(1-아세톡시-2-플루오로-n-부틸)-N-[(4,6-디메톡시피리미딘-2-일)아미노카르보닐]벤젠술폰아미드 2g을 테트라히드로퓨란 60㎖에 녹이고 여기에 수산화리튬 08g과 물 10㎖을 넣는다.2 g of erythro-2- (1-acetoxy-2-fluoro-n-butyl) -N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] benzenesulfonamide was added to tetrahydrofuran. Dissolve in 60 ml, and add 08 g of lithium hydroxide and 10 ml of water.
실온에서 12시간 교반 후에 0℃에서 염산으로 산성화시킨다. 반응액을 100㎖의 에틸 아세테이트로 희석하고 물로 1회 세척한다.After stirring for 12 hours at room temperature, acidified with hydrochloric acid at 0 ° C. The reaction solution is diluted with 100 ml of ethyl acetate and washed once with water.
유기층을 황산마그네슘으로 건조하여 여과하고 농축시키고 이 잔사를 에틸 에테르와 헥산으로 잘 처리하여 목적화합물 1.7g을 백색고체로 얻었다.The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was well treated with ethyl ether and hexane to obtain 1.7 g of the target compound as a white solid.
녹는점(℃):101~104Melting Point (℃): 101-104
H NMR(200MHz, CDCl):δ H NMR (200 MHz, CDCl): δ
0.95(t,3H,J=8Hz),1.57~1.87(m,2H),3.86~3.92(brs,1H),0.95 (t, 3H, J = 8 Hz), 1.57-1.87 (m, 2H), 3.86-3.92 (brs, 1H),
3.96(s,6H),4.58~4.90(m,1H),5.76(s,1H),5.79~6.00(m,3H),3.96 (s, 6H), 4.58 ~ 4.90 (m, 1H), 5.76 (s, 1H), 5.79 ~ 6.00 (m, 3H),
7.27~8.16(m,5H), 12.83(brs,1H).7.27-8.16 (m, 5H), 12.83 (brs, 1H).
IR(KBr)ν(C=O)1710㎝ IR (KBr) ν (C = O) 1710 cm
[실시예 7]Example 7
본 발명의 화합물의 제초효과는 온실시험에서 발견되었으며 그 시험방법은 다음과 같다.Herbicidal effect of the compound of the present invention was found in the greenhouse test and the test method is as follows.
발아전 처리시험Pre-germination Treatment Test
활성화합물 1중량부를 아세톤 5중량부와 유화제로써 알킬아릴 폴리글리콜 에테르 1중량부에 섞고 녹인후 물로 원하는 농도로 희석하여 적절한 제제를 만든다.1 part by weight of the active compound is mixed with 5 parts by weight of acetone and 1 part by weight of an alkylaryl polyglycol ether as an emulsifier, dissolved, and diluted with water to a desired concentration to prepare a suitable formulation.
시험할 식물의 씨앗을 통상의 토양에 심고 24시간 후에 활성화합물을 함유하 제제를 뿌려준다.The seeds of the plants to be tested are planted in normal soil and after 24 hours the preparations are sprayed with the active compound.
이때 단위면적당 뿌려주는 물의 양을 일정하게 하는 것이 좋다. 또한 제제에 포함된 활성화합물의 농도는 중요하지 않으며, 단지 단위면적당 뿌려주는 활성화합물의 양이 중요하다.At this time, it is good to make constant the amount of water sprayed per unit area. In addition, the concentration of the active compound in the formulation is not important, only the amount of active compound sown per unit area is important.
약제처리 3주후에 식물의 손상정도를 약제를 처리하지 않은 대조구와 비교하여 손상 %로 평가하여 나타낸다.Three weeks after drug treatment, the degree of damage to the plant is assessed as a percentage of damage compared to the control without treatment.
평가수치는 다음과 같이 나타낸다.The evaluation value is expressed as follows.
0% = 무효력(약제처리 하지 않은 것과 같음)0% = invalid force (same as unpharmaceutical)
20% = 약간의 효과20% = slight effect
70% = 제초효과70% = herbicide
100% = 전멸(완전고사)100% = annihilation (completed test)
이 시험에서 예를 들자면 실시예에 있는 일반식(Ⅰ) 화합물은 단자엽이나 쌍자엽 잡초를 제어하는데에 매우 좋은 효과를 나타내었다.In this test, for example, the compound of formula (I) in the example showed a very good effect in controlling monocotyledonous or dicotyledonous weeds.
[실시예 8]Example 8
발아후 처리시험Post-germination treatment test
활성화합물 1중량부를 5중량부의 아세톤과 1중량부의 실시예 26의 유화제의 혼합물에 녹이고 물로 원하는 농도로 희석하여 적절한 제제를 만든다.1 part by weight of the active compound is dissolved in a mixture of 5 parts by weight of acetone and 1 part by weight of the emulsifier of Example 26 and diluted to the desired concentration with water to form a suitable formulation.
키가 5-15㎝되는 시험식물에 활성화합물을 함유하는 상기의 제제를 스프레이로 단위면적당 활성화합물의 양이 원하는 양이 되도록 뿌려준다. 스프레이하는 액제의 활성성분 농도는 헥타당 물 2000ℓ로 뿌렸을때 활성화합물의 양이 원하는 특정 양이 되도록 선택한다. 3주 후에 식물의 손상 정도를 약제를 처리하지 않은 대조구와 비교하여 손상 %로 평가하여 나타낸다. 평가수치는 다음과 같이 나타낸다.Spray the above formulation containing the active compound to the test plants 5-15 cm tall so that the desired amount of active compound per unit area is sprayed. The active ingredient concentration of the sprayed solution is chosen so that the amount of active compound is the desired amount when sprayed with 2000 liters of water per hectare. After 3 weeks, the degree of damage to the plant is expressed as percentage damage compared to the control without treatment. The evaluation value is expressed as follows.
0% = 무효과(약제처리 하지 않은 것과 같음)0% = invalid (same as unpharmaceutical)
20% = 약간의 효과20% = slight effect
70% = 제 초효과70% = herbicidal effect
100% = 전멸(완전고사)100% = annihilation (completed test)
이 시험에서 예를 들자면 실시예에 있는 일반식(Ⅰ) 화합물은 단자엽이나 쌍자엽 잡초를 제어하는데에 매우 좋은 효과를 나타내었다.In this test, for example, the compound of formula (I) in the example showed a very good effect in controlling monocotyledonous or dicotyledonous weeds.
[실시예 9]Example 9
담수처리시험Desalination Test
60㎠ 또는 140㎠의 원형폿트에 비료를 소량 넣고 곤죽상태의 멸균된 논흙을 5㎝ 깊이로 담는다. 논피, 알방동산이, 사마귀풀, 물달개비, 마디꽃, 여뀌바늘, 올챙이고랭이, 말뚝외풀 등의 종자와 너도방동산이, 올미 등의 다년생 영양채를 토양표층에 혼입 또는 재식하고 미리 육묘해 둔 벼의 묘(2~3엽기)를 폿트당 1본씩 2㎝ 깊이로 심는다.A small amount of fertilizer is placed in a round pot of 60 cm2 or 140 cm2, and the sterilized paddy soil is placed 5 cm deep. Seeds such as paddy fields, eggplants, mantis grass, mantis grass, knotweed flowers, yellow needles, tadpoles, and pistils, and perennial nutrients such as nami are mixed or planted in the soil surface and seeded. Plant seedlings (2 ~ 3 leaves) of rice, 2cm deep, one per pot.
이식한 후 2㎝ 깊이로 담수하여 1일간 둔 다음 밭조건내에서와 같이 조제된 약제를 골고루 점적처리한다(4㎏/ha 수준일 경우는 폿트당 4㎎). 약제처리 후 2주째 밭조건과 동일한 조사기준에 의하여 제초활성을 조사한다.After transplantation, 2 cm of fresh water is allowed to stand for 1 day, and then the medicines prepared as in field conditions are evenly applied (4 mg per pot at 4 kg / ha). At 2 weeks after treatment, herbicidal activity was examined according to the same survey criteria as field conditions.
상기의 실시예들은 대표적 예로써 설명된 것이며 본 발명이 실시예에 표현된 특정예에만 국한되는 것은 아니다.The above embodiments are described as representative examples and the present invention is not limited to the specific examples represented in the embodiments.
*DAY AFTER TREATMENT* DAY AFTER TREATMENT
Claims (13)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019940027152A KR0140020B1 (en) | 1994-10-24 | 1994-10-24 | Herbicidal sulfonamide derivatives |
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| KR1019940027152A KR0140020B1 (en) | 1994-10-24 | 1994-10-24 | Herbicidal sulfonamide derivatives |
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