TW201348217A - Herbicidally active sulfin-and sulfonimidoylbenzamides - Google Patents
Herbicidally active sulfin-and sulfonimidoylbenzamides Download PDFInfo
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本發明乃有關除草劑之技術領域，特別是有關用於選擇性控制有用植物作物之濶葉葉片及雜草之除草劑之技術領域。 The present invention relates to the technical field of herbicides, and more particularly to the technical field of herbicides for controlling leaf blades and weeds of useful plant crops.
WO 2011/035874 A1揭示具除草活性之N-(1,2,5-二唑-3-基)苯甲醯胺類。從歐洲專利申請案EP10174893(該申請案具有早於本發明之優先權日，惟於本發明優先權日時尚未公告)已知，特定之N-(四唑-5-基)-與N-(***-5-基)苯甲醯胺類及-菸鹼醯胺作為除草劑。然而，彼等公告案中所述化合物之除草活性及/或作物植物相容性不一定充足。 WO 2011/035874 A1 discloses N-(1,2,5- with herbicidal activity Diazol-3-yl)benzamide. It is known from the European patent application EP10174893 (which has a priority date earlier than the present invention, but not yet announced on the priority date of the present invention), specific N-(tetrazol-5-yl)- and N-( Triazol-5-yl)benzamide and nicotine amide as herbicides. However, the herbicidal activity and/or crop plant compatibility of the compounds described in their announcements are not necessarily sufficient.
本發明之目的在於提供相較於先前技藝中已知化合物具增進性質之具除草活性之化合物。 It is an object of the present invention to provide herbicidal compounds which have improved properties compared to compounds known in the prior art.
頃發現，特定之亞磺醯-及磺醯亞胺醯基苯甲醯胺類特別適合作為除草劑。因此，本發明提供具下式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類及其鹽
於式(I)及下文所示所有化學式中，具有兩個以上碳原子之烷基可為直鏈或分支鏈；烷基為，例如，甲基、乙基、正-或異丙基、正-、異-、第三-或2-丁基、戊基、己基如正己基、異己基與1,3-二甲基丁基。同理，烯基為，例如，烯丙基、1-甲基丙 -2-烯-1-基、2-甲基丙-2-烯-1-基、丁-2-烯-1-基、丁-3-烯-1-基、1-甲基-3-烯-1-基與1-甲基丁-2-烯-1-基。炔基為，例如，炔丙基、丁-2-炔-1-基、丁-3-炔-1-基、1-甲基丁-3-炔-1-基。於各情形下，複鍵可位於不飽和基團之任何位置。環烷基為具三至六個碳原子之碳環飽和環系，例如環丙基、環丁基、環戊基或環己基。同理，環烯基為具三至六個碳環員之單環烯基，例如環丙烯基、環丁烯基、環戊烯基與環己烯基，其中雙鍵可位於任何位置。 In the formula (I) and all of the formulas shown below, the alkyl group having two or more carbon atoms may be a straight or branched chain; the alkyl group is, for example, a methyl group, an ethyl group, a n- or isopropyl group, or a positive -, iso-, tri- or 2-butyl, pentyl, hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, an alkenyl group is, for example, allyl, 1-methylpropane. 2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-3- Alk-1-yl and 1-methylbut-2-en-1-yl. The alkynyl group is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. In each case, the complex bond can be located anywhere in the unsaturated group. The cycloalkyl group is a carbocyclic saturated ring system having three to six carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group. Similarly, a cycloalkenyl group is a monocycloalkenyl group having three to six carbon ring members, such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group, wherein the double bond can be located at any position.
鹵素為氟、氯、溴或碘。 Halogen is fluorine, chlorine, bromine or iodine.
雜環基為飽和、部分飽和或完全不飽和之環狀基團，其包含3至6個環原子(其中1至4個得自包括氧、氮與硫之組群)，可附加地與苯并環稠合。雜環基為，例如，哌啶基、吡咯啶基、四氫呋喃基、二氫呋喃基與氧呾基。 A heterocyclic group is a saturated, partially saturated or fully unsaturated cyclic group comprising from 3 to 6 ring atoms (one to four of which are derived from a group comprising oxygen, nitrogen and sulfur), additionally with benzene The ring is fused. The heterocyclic group is, for example, piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl and oxonyl.
雜芳基為芳族環狀基團，其包含3至6個環原子(其中1至4個得自包括氧、氮與硫之組群)，可附加地與苯并環稠合。雜芳基為，例如，苯并咪唑-2-基、呋喃基、咪唑基、異唑基、異噻唑基、唑基、吡基、嘧啶基、嗒基、吡啶基、苯并異唑基、噻唑基、吡咯基、吡唑基、噻吩基、1,2,3-二唑基、1,2,4-二唑基、1,2,5-二唑基、1,3,4-二唑基、1,2,4-***基、1,2,3-***基、1,2,5-***基、1,3,4-***基、1,2,4-***基、1,2,4-噻二唑基、1,3,4-噻二唑基、1,2,3-噻二唑基、1,2,5-噻二唑基、2H-1,2,3,4-四唑基、1H-1,2,3,4-四唑基、1,2,3,4-***基、1,2,3,5-***基、1,2,3,4-噻***基與1,2,3,5-噻***基。 The heteroaryl group is an aromatic cyclic group containing 3 to 6 ring atoms (1 to 4 of which are derived from a group including oxygen, nitrogen and sulfur), and may be additionally fused to a benzo ring. Heteroaryl is, for example, benzimidazol-2-yl, furyl, imidazolyl, iso Azyl, isothiazolyl, Azolyl, pyridyl Base, pyrimidinyl, oxime Base, pyridyl, benzo Azyl, thiazolyl, pyrrolyl, pyrazolyl, thienyl, 1,2,3- Diazolyl, 1,2,4- Diazolyl, 1, 2, 5- Diazolyl, 1,3,4- Diazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl, 1,2,4- Triazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, 2H- 1,2,3,4-tetrazolyl, 1H-1,2,3,4-tetrazolyl, 1,2,3,4- Triazolyl, 1, 2, 3, 5- Triazolyl, 1,2,3,4-thiatriazolyl and 1,2,3,5-thiatriazole.
若一基團經多個基團取代，意指該基團經一或多個相同或不同之所述基團取代；此同理適用於得自不同原子與元素 的環系之建構。於此，在標準溫度及壓力條件下，熟習此項技藝者已知其不具化學穩定性之化合物不包括於申請專利範圍之內。 If a group is substituted with a plurality of groups, it means that the group is substituted by one or more of the same or different groups; the same applies to different atoms and elements. The construction of the ring system. Here, under standard temperature and pressure conditions, compounds known to those skilled in the art to be non-chemically stable are not included in the scope of the patent application.
視取代基之性質及連接而定，式(I)化合物可呈立體異構物存在。如果，例如，出現一或多個經不對稱取代之碳原子，則可能存在鏡像異構物及非鏡像異構物。當S(O)n基團中之n為1(亞碸類)時，亦存在立體異構物。此外，碸亞胺基或烴基硫亞胺基中之硫原子為掌性中心。立體異構物可利用習知分離方法(例如利用層析分離程序)，從製備中製得之混合物獲得；亦可使用光學活性起始物質及/或助劑，利用立體選擇反應，選擇性地製備立體異構物。本發明亦有關式(I)所包含惟未示出其特定立體型之所有立體異構物，及其混合物。本發明亦有關式(I)所包含惟未具體界定之所有E/Z異構物，及其混合物。 Depending on the nature of the substituent and the linkage, the compound of formula (I) may exist as a stereoisomer. If, for example, one or more asymmetrically substituted carbon atoms are present, there may be mirror image isomers and non-an image isomers. Stereoisomers are also present when n in the S(O) n group is 1 (anthracene). Further, the sulfur atom in the sulfhydrido group or the hydrocarbyl sulfilimine group is a palmitic center. Stereoisomers can be obtained from conventionally prepared separation methods (for example, using a chromatographic separation procedure), or optically active starting materials and/or auxiliaries, using stereoselective reactions, optionally Stereoisomers were prepared. The invention also relates to all stereoisomers of formula (I) which are not shown to be specific stereotypes thereof, and mixtures thereof. The invention also relates to all E/Z isomers of formula (I) which are not specifically defined, and mixtures thereof.
式(I)化合物能形成鹽；使鹼與帶有酸性氫原子(例如於R"之情形下)之彼等式(I)化合物作用，則可形成鹽。適當鹼為，例如，有機胺如三烷胺、嗎福啉、哌啶或吡啶，以及銨、鹼金屬或鹼土金屬氫氧化物、碳酸鹽與碳酸氫鹽，特別是氫氧化鈉與氫氧化鉀、碳酸鈉與碳酸鉀及碳氫酸鈉與碳酸氫鉀。彼等鹽為其中酸性氫被農業上適當之陽離子置換之化合物，例如金屬鹽，特別是鹼金屬鹽或鹼土金屬鹽，尤其是鈉鹽與鉀鹽，或者銨鹽、與有機胺之鹽或四級銨鹽，例如與式[NRR*R**R***]+陽離子之鹽，其中R、R*、R**與R***互相獨立地各代表有機基團，特別是烷基、芳基、芳烷基或烷芳基。亦適當者為烷基鋶鹽與烷基亞碸鎓鹽如(C1-C4)-三烷基鋶鹽及(C1-C4)-三烷基亞碸鎓鹽。 The compound of the formula (I) is capable of forming a salt; a salt can be formed by reacting a base with a compound of the formula (I) having an acidic hydrogen atom (for example, in the case of R " . A suitable base is, for example, an organic amine such as Trialkylamine, morphine, piperidine or pyridine, and ammonium, alkali or alkaline earth metal hydroxides, carbonates and hydrogencarbonates, especially sodium hydroxide and potassium hydroxide, sodium carbonate and potassium carbonate and hydrocarbons Sodium sulphate and potassium hydrogencarbonate. These salts are compounds in which acidic hydrogen is replaced by suitable cations in agriculture, such as metal salts, especially alkali metal or alkaline earth metal salts, especially sodium and potassium salts, or ammonium salts, a salt with a metal amine or a quaternary ammonium salt, for example, a salt of the formula [NRR*R**R***] + cation, wherein R, R*, R** and R*** each independently represent an organic a group, especially an alkyl group, an aryl group, an arylalkyl group or an alkylaryl group. Also suitable are alkyl phosphonium salts and alkyl phosphonium salts such as (C 1 -C 4 )-trialkylsulfonium salts and C 1 -C 4 )-trialkylarylene salt.
於鹼性基團(例如，舉例而言，胺基、烷胺基、二烷 胺基、N-哌啶基、N-嗎福啉基或N-吡啶基)處，利用與適當無機酸或有機酸形成加合物，式(I)化合物能形成鹽；其中無機酸例如HCl、HBr、H2SO4、H3PO4或HNO3，有機酸例如羧酸如甲酸、乙酸、丙酸、草酸、乳酸或柳酸，或磺酸例如對甲苯磺酸。於此情形下，該鹽含有酸之共軛鹼作為陰離子。 At a basic group (for example, an amine group, an alkylamino group, a dialkylamino group, an N-piperidinyl group, an N-norporinyl group or an N-pyridyl group), and a suitable inorganic acid or The organic acid forms an adduct, and the compound of formula (I) is capable of forming a salt; wherein a mineral acid such as HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , an organic acid such as a carboxylic acid such as formic acid, acetic acid, propionic acid, Oxalic acid, lactic acid or hydrochloric acid, or a sulfonic acid such as p-toluenesulfonic acid. In this case, the salt contains a conjugate base of an acid as an anion.
較佳者為如下界定之式(I)化合物，其中Q 為Q1、Q2、Q3或Q4基團，
特佳者為如下界定之式(I)化合物，其中Q 為Q1、Q2、Q3或Q4基團，
Q為Q1或Q2之根據本發明化合物可，舉例而言，起初於式(I-硫醚)之硫醚階段，使用反應圖示1所示方法，利用苯甲醯氯(II)與5-胺基-1-H-1,2,4-***或5-胺基-1H-四唑(III)之鹼催化反應，逐步製備；該等硫醚中間體接著可根據反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the invention wherein Q is Q1 or Q2 may, for example, be initially in the thioether phase of formula (I-thioether), using the method shown in Scheme 1, using benzamidine chloride (II) and 5- Base-catalyzed reaction of amino-1-H-1,2,4-triazole or 5-amino-1H-tetrazole (III); the thioether intermediates can then be according to the reaction scheme 13, Conversion to the sulfinium- and sulfonimide-mercaptobenzamides of the formula (I) according to the invention.
Q為Q1或Q2之根據本發明化合物亦可，舉例而言，起初於式(I-硫醚)之硫醚階段，使用反應圖示2所示方法，使式(IV)之苯甲酸與5-胺基-1-H-1,2,4-***或5-胺基-1H-四唑(III)反應，逐步製備；該等硫醚中間體接著可根據反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the invention wherein Q is Q1 or Q2 may, for example, be initially in the thioether phase of formula (I-thioether), using the method shown in Scheme 2, to give benzoic acid of formula (IV) with 5 -Amino-1-H-1,2,4-triazole or 5-amino-1H-tetrazole (III) reaction, stepwise preparation; these thioether intermediates can then be converted to The sulfinium- and sulfonimide-mercaptobenzamides of the formula (I) according to the invention.
關於活化，可使用習知用於醯胺化反應之試劑例如，舉例而言，1,1`-羰基二咪唑(CDI)、二環己基-碳二亞胺(DCC)、2,4,6-三氧化2,4,6-三丙基-1,3,5,2,4,6-三氧雜三膦烷(trioxatriphosphinane)(T3P)。 As the activation, a reagent conventionally used for the guanidation reaction can be used, for example, 1,1'-carbonyldiimidazole (CDI), dicyclohexyl-carbodiimide (DCC), 2, 4, 6 - Tris(3,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane (T3P).
為基底之式(II)苯甲醯氯類及式(IV)苯甲酸類原則上為已知化合物，可根據例如見述於WO 03/014071 A1、WO 2008/125214 A1、WO 2011/12246 A1及WO 2011/012247 A1之方法製備。 The benzamidine chlorides of the formula (II) and the benzoic acid of the formula (IV) are, in principle, known compounds, which can be described, for example, in WO 03/014071 A1, WO 2008/125214 A1, WO 2011/12246 A1. And prepared by the method of WO 2011/012247 A1.
Q為Q1或Q2之根據本發明化合物亦可根據反應圖示3中敘述之方法，使N-(1H-1,2,4-***-5-基)苯甲醯胺或N-(1H-四唑-5-基)苯甲醯胺反應予以製備：
關於反應圖示3中所示反應，可於鹼存在下，使用例如烷化劑，如烷基鹵化物、烷基磺酸酯或二烷基硫酸酯。 With regard to the reaction shown in Reaction Scheme 3, for example, an alkylating agent such as an alkyl halide, an alkyl sulfonate or a dialkyl sulfate may be used in the presence of a base.
式(III)之5-胺基-1H-四唑類係市售可得或者可類似於文獻中之已知方法予以製備。經取代之5-胺基四唑類，舉例而言，可利用見述於Journal of the American Chemical Society (1954),76,923-924之方法，以胺基四唑製備：
上述反應中，X為脫離基例如碘。經取代之5-胺基四唑類亦可，舉例而言，如Journal of the American Chemical Society (1954)76,88-89中所述，予以合成：
式(III)之5-胺基-1H-***類係市售可得或者可類似
於文獻中之已知方法予以製備。經取代之5-胺基***類，舉例而言，可利用見述於Zeitschrift für Chemie(1990),30(12),436-437之方法，以胺基***製備：
經取代之5-胺基***類亦可，舉例而言，如Chemische Berichte(1964),97(2),396-404中所述予以合成：
經取代之5-胺基***類亦可，舉例而言，如Angewandte Chemie(1963),75,918中所述予以合成：
Q為Q3之根據本發明化合物可，舉例而言，起初於式(I-硫醚)之硫醚階段，根據反應圖示4所示方法，利用苯甲醯氯(II)與4-胺基-1,2,5-二唑(VI)之鹼催化反應，逐步製備；該等硫醚中間體可依照反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the present invention wherein Q is Q3 may, for example, be initially used in the thioether phase of the formula (I-thioether), according to the method shown in Scheme 4, using benzamidine chloride (II) and 4-amino group. -1,2,5- The base of the oxadiazole (VI) is catalyzed and gradually prepared; the intermediates of the thioethers can be converted into the sulfinium- and sulfonimide-based benzhydrazides according to the formula (I) according to the reaction scheme 13 of the present invention. Amines.
根據本發明化合物亦可，起初於式(I-硫醚)之硫醚階段，根據反應圖示5所示方法，使式(IV)苯甲酸與4-胺基-1,2,5-二唑(VI)反應，逐步製備；該等硫醚中間體可依照反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the invention may also be initially subjected to the thioether phase of the formula (I-thioether) according to the method shown in Scheme 5, such that the benzoic acid of formula (IV) and 4-amino-1,2,5- The oxadiazole (VI) reaction is carried out stepwise; the thioether intermediates can be converted into the sulfinium- and sulfonimide-mercaptobenzamides according to the formula (I) according to the reaction scheme 13.
關於活化，可使用習知用於醯胺化反應之試劑例如，舉例而言，1,1`-羰基二咪唑(CDI)、二環己基-碳二亞胺(DCC)、2,4,6-三氧化2,4,6-三丙基-1,3,5,2,4,6-三氧雜三膦烷(T3P)。 As the activation, a reagent conventionally used for the guanidation reaction can be used, for example, 1,1'-carbonyldiimidazole (CDI), dicyclohexyl-carbodiimide (DCC), 2, 4, 6 - 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphane (T3P).
式(VI)之4-胺基-1,2,5-二唑類係市售可得或已知或可類似於文獻中之已知方法予以製備。 4-amino-1,2,5- of formula (VI) The oxazolines are either commercially available or known or can be prepared analogously to methods known in the literature.
3-烷基-4-胺基-1,2,5-二唑類，舉例而言，可利用見述於Russian Chemical Bulletin,Int.Ed.,Vol.54,No.4,S.1032-1037(2005)之方法，以ß-酮酸酯類製備：
3-芳基-4-胺基-1,2,5-二唑類可，舉例而言，如Russian Chemical Bulletin,54(4),1057-1059,(2005)或Indian Journal of Chemistry,Section B：Organic Chemistry Including Medicinal Chemistry,26B(7),690-2,(1987)中所述予以合成：
3-胺基-4-鹵基-1,2,5-二唑類可，舉例而言，利用見述於Heteroatom Chemistry 15(3),199-207(2004)之方法，以市售可
得之3,4-二胺基-1,2,5-二唑，經由山德邁耳(Sandmeyer)反應予以製備：
親核基團RY可如Journal of Chemical Research,Synopses,(6),190,1985或Izvestiya Akademii Nauk SSSR,Seriya Khimicheskaya,(9),2086-8,1986或***化學公報(Izvestiya Akademii Nauk,Seriya Khimicheskaya),53(3),596-614,2004中所述，經由置換3-胺基-1,2,5-二唑類中之脫離基L而被引入。L為脫離基例如，舉例而言，氯、溴、碘、甲磺醯氧基、甲苯磺醯氧基、三氟磺醯氧基等。 The nucleophilic group R Y can be as described in Journal of Chemical Research, Synopses, (6), 190, 1985 or Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, (9), 2086-8, 1986 or Russian Chemical Bulletin (Izvestiya Akademii Nauk, Seriya Khimicheskaya), 53(3), 596-614, 2004, via substitution of 3-amino-1,2,5- The azole is introduced into the cleavage group L. L is a leaving group, for example, chlorine, bromine, iodine, methanesulfonyloxy, toluenesulfonyloxy, trifluorosulfonyloxy or the like.
Q為Q4之根據本發明化合物可，舉例而言，起初於式(I-硫醚)之硫醚階段，根據反應圖示6所示方法，利用苯甲醯氯(II)與2-胺基-1,3,4-二唑(VII)之鹼催化反應，逐步製備；該等硫醚中間體接著可依照反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the present invention wherein Q is Q4 may, for example, be initially used in the thioether phase of the formula (I-thioether), according to the method shown in Scheme 6, using benzamidine chloride (II) and 2-amino group. -1,3,4- The base of the oxadiazole (VII) catalyzes the reaction and is gradually prepared; the thioether intermediate can then be converted into the sulfinium- and sulfonimide-based benzophenone according to the formula (I) according to the reaction scheme 13 Amidoxis.
根據本發明之化合物亦可，起初於式(I-硫醚)之硫醚階段，根據反應圖示7所示方法，使式(IV)之苯甲酸與2-胺基-1,3,4-二唑(VII)反應，逐步製備；該等硫醚中間體接著可依照反應圖示13，轉化為根據本發明之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the invention may also be initially subjected to the thioether phase of the formula (I-thioether) to give the benzoic acid of the formula (IV) and the 2-amino-1,3,4 according to the method shown in Scheme 7. - The oxazol (VII) reaction is carried out stepwise; the thioether intermediates can then be converted to the sulfinium- and sulfonimide benzylbenzamides according to the invention according to Scheme 13.
關於活化，可使用習知用於醯胺化反應之試劑例如，舉例而言，1,1`-羰基二咪唑(CDI)、二環己基-碳二亞胺(DCC)、2,4,6-三氧化2,4,6-三丙基-1,3,5,2,4,6-三氧雜三膦烷(T3P)。 As the activation, a reagent conventionally used for the guanidation reaction can be used, for example, 1,1'-carbonyldiimidazole (CDI), dicyclohexyl-carbodiimide (DCC), 2, 4, 6 - 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphane (T3P).
R”取代基不為氫之根據本發明化合物可，舉例而如，根據反應圖示8所示方法，使N-(1,2,5-二唑-3-基)-、N-(1,3,4-二唑-2-基)-、N-(四唑-5-基)-或N-(***-5-基)-芳基羧醯胺(I)與式(VIII)化合物(其中L為脫離基例如，舉例而言，氯、溴、碘、甲磺醯氧基、甲苯磺醯氧基、三氟磺醯氧基等)反應予以製備：
式(VIII)化合物係市售可得或者可利用見述於文獻之已知方法製備。 Compounds of formula (VIII) are either commercially available or can be prepared by known methods described in the literature.
根據本發明之化合物亦可，起初於式(I-硫醚)之硫醚階段，舉例而言，如J.Het：Chem.(1972),9(1),107-109中所述，根據反應圖示9所示方法，使式(IX)之胺與醯基氯(II)反應，逐步製備；該等硫醚中間體接著可依照反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compounds according to the invention may also be initially in the thioether phase of the formula (I-thioether), for example as described in J. Het: Chem. (1972), 9(1), 107-109, The reaction shown in Figure 9 is carried out by reacting an amine of the formula (IX) with mercaptochloro(II) and preparing it stepwise; the thioether intermediate can then be converted into the formula (I) according to the invention according to the reaction scheme 13 Sulfosene- and sulfonimide-mercaptobenzamide.
根據本發明之化合物亦可，起初於式(I-硫醚)之硫醚階段，根據反應圖示10所示方法，使式(IX)之胺與式(IV)之酸反應，逐步製備；該等硫醚中間體接著可依照反應圖示13，轉化為根據本發明式(I)之亞磺醯-及磺醯亞胺醯基苯甲醯胺類。 The compound according to the present invention may also be initially reacted with an acid of the formula (IV) according to the method shown in Scheme 10, starting from the thioether phase of the formula (I-thioether), and gradually prepared; The thioether intermediates can then be converted to the sulfinium- and sulfonimide fluorenylbenzamides of formula (I) according to the invention according to Scheme 13.
關於活化，可使用習知用於醯胺化反應之試劑例如，舉例而言，1,1`-羰基二咪唑(CDI)、二環己基-碳二亞胺(DCC)、2,4,6-三氧化2,4,6-三丙基-1,3,5,2,4,6-三氧雜三膦烷(T3P)。 As the activation, a reagent conventionally used for the guanidation reaction can be used, for example, 1,1'-carbonyldiimidazole (CDI), dicyclohexyl-carbodiimide (DCC), 2, 4, 6 - 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphane (T3P).
式(IX)之胺係市售可得或從文獻中已知或可，舉例而如，利用見述於反應圖示11之方法進行鹼催化之烷化反應或還原性胺化反應，或利用見述於反應圖示12之方法，以胺R”-NH2進行脫離基L之親核性置換(其中L為脫離基例如，舉例而言，氯、溴、碘、甲磺醯氧基、甲苯磺醯氧基、三氟磺醯氧基等)予以製備：
式(IX)之胺亦可，舉例而言，於Q=Q1時，如J.Org.Chem.73(10),3738-3744(2008)中所述，或於Q=Q4時，如Buletinul Institutului Politehnic din lasi(1974),20(1-2),95-99或J.Org.Chem.67(21),7361-7364(2002)中所述，利用環化反應製備。 The amine of formula (IX) can also be, for example, when Q = Q1, as described in J. Org. Chem. 73 (10), 3738-3744 (2008), or at Q = Q4, such as Buletinul. Institutului Politehnic din lasi (1974), 20(1-2), 95-99 or J. Org. Chem. 67 (21), 7361-7364 (2002), prepared by a cyclization reaction.
根據本發明之式(I)化合物可由式(I-硫醚)對應之硫醚類製備(反應圖示13)。欲達此目的，舉例而言，以氰胺及氧化劑 [二乙醯氧碘苯(iodosobenzene diacetate)、次氯酸鈉或N-溴琥珀醯亞胺]使硫醚轉化為對應之硫亞胺，其進一步氧化成為磺醯亞胺。適用於氧化成為磺醯亞胺之氧化劑為例如，舉例而言，間氯過苯甲酸、過錳酸鈉或過碘酸鈉與三氯化釕之混合物。NH-磺醯亞胺類可，舉例而言，使用疊氮化鈉與硫酸，以亞碸類製得；並可於氮原子處以試劑(例如，舉例而言，溴化氰、醯基氯或酸酐類、氯甲酸酯類、硝酸或其他化合物)官能化。N-磺酸化硫亞胺類成為對應磺醯亞胺類之氧化反應，舉例而言，可以氫達成。替代地，亞碸類可轉化成為N-醯基化或N-磺酸化之磺醯亞胺類。然後，該羧醯胺或磺醯胺分別可裂解得到NH-磺醯亞胺。此外，由硫醚類產生硫亞胺類及磺醯亞胺類、或由亞碸類產生磺醯亞胺類、或衍生化硫亞胺類與磺醯亞胺類以及NH-磺醯亞胺類之該等合成方法見述於，例如，C.Org.Lett.2004,6,1305；Bolm,C.Org.Lett.2007,9,3809；Bolm,C.Synthesis 2010,17,2922；Bolm,C.Adv.Synth.Catal.2010,352,309；WO 2007/095229、WO 2008/141843、US 2008/0207910、US 2008/0194634與US 2010/0056534中。 The compound of the formula (I) according to the invention can be prepared from the thioethers of the formula (I-thioether) (reaction shown in Figure 13). For this purpose, for example, cyanamide and oxidizing agents [iodosobenzene diacetate, sodium hypochlorite or N-bromosuccinimide] converts the thioether to the corresponding sulfilimine, which is further oxidized to the sulfoximine. An oxidizing agent suitable for oxidation to sulfonimide is, for example, a mixture of m-chloroperbenzoic acid, sodium permanganate or sodium periodate and antimony trichloride. NH-sulfonimides may, for example, be prepared using an azide such as sodium azide and sulfuric acid; and may be reagents at the nitrogen atom (for example, cyanogen bromide, mercapto chloride or Anhydrides, chloroformate, nitric acid or other compounds) are functionalized. The N-sulfonated sulfilimines are oxidized by the corresponding sulfonimides, and can be achieved, for example, by hydrogen. Alternatively, the fluorenes can be converted to N-thiolated or N-sulfonated sulfonimides. The carboxamide or sulfonamide can then be cleaved separately to give NH-sulphonimine. In addition, thioimines and sulfonimides are produced from thioethers, or sulfoximines are produced from fluorenes, or sulfilimines and sulfonimines and NH-sulfonimides are derived. Such synthetic methods of the class are described, for example, in C. Org. Lett. 2004, 6, 1305; Bolm, C. Org. Lett. 2007, 9, 3809; Bolm, C. Synthesis 2010, 17, 2922; C. Adv. Synth. Catal. 2010, 352, 309; WO 2007/095229, WO 2008/141843, US 2008/0207910, US 2008/0194634 and US 2010/0056534.
如果需要，則該等合成序列必須使用保護基以達成足夠之選擇性；特別是原則上與醯胺氮原子之相似官能化競爭之NH-磺醯亞胺之官能化。 If desired, such synthetic sequences must employ a protecting group to achieve sufficient selectivity; in particular, functionalization of NH-sulfonimide which in principle competes with similar functionalization of the guanamine nitrogen atom.
改變反應步驟順序亦可為權宜之計。因此，帶有亞碸之苯甲酸類不直接轉化為其醯基氯；於此，較有利為於硫醚階段最初形成醯胺，然後氧化該硫醚成為亞碸。於特定條件下，磺醯亞胺類及特別是硫亞胺類不夠穩定(Bolm,C.Adv.Synth.Catal.2010,352,309)，因此可如上文諸反應圖示所示，起初於硫醚階段合成苯甲醯胺，僅於合成順序最後，由該硫醚產生硫亞胺或磺醯亞胺較為有利。然而，於夠穩定之情形下，視取代方式而定，於苯甲酸階段(或甚至在更早階段)，先由硫醚產生磺醯亞胺之硫亞胺，然後才將苯甲酸轉化為其醯胺亦有利。 Changing the sequence of reaction steps can also be a stopgap measure. Therefore, the benzoic acid with anthracene is not directly converted to its mercapto chloride; however, it is advantageous to initially form a decylamine in the thioether stage and then oxidize the thioether to an amidoxime. Under certain conditions, sulfoximines and especially sulfilimines are not sufficiently stable (Bolm, C. Adv. Synth. Catal. 2010, 352, 309) and can therefore be initially represented by thioethers as shown in the above reaction schemes. The synthesis of benzamide in the stage is advantageous only for the production of sulfilimine or sulfoximine from the thioether at the end of the synthesis sequence. However, in the case of stability, depending on the mode of substitution, in the benzoic acid stage (or even at an earlier stage), the sulfinimide sulfilimine is first produced from the thioether, and then the benzoic acid is converted to Indoleamine is also beneficial.
於特定情形下，反應中不使用游離苯甲酸而使用其衍生物可能有利。有時，官能基只於酸性或只於鹼性介質中操作(亦即只以游離苯甲酸或只以其鹽操作)，其穩定性即足夠。許多情形下，以例如甲酯或乙酯等酯類為適當。第三丁酯類經常有效地於空間上防護羧基對抗親核試劑，且容易在酸性介質中裂解(T.W.Greene,P.G.M.Wuts,Protective Groups in Organic Synthesis,2nd Edition,John Wiley & Sons,Inc.1991,p.227 ff.)。亦適當者為較羧基穩定相當多之基團，然而，彼等亦易於再轉化成為游離羧酸；包括，例如，唑啉類(T.W.Greene,P.G.M.Wuts,Protective Groups in Organic Synthesis,2nd Edition,John Wiley & Sons,Inc.1991,p.265 ff.；Z.Hell et al.,Tetrahedron Letters 43(2002),3985-3987)。 In certain cases, it may be advantageous to use free benzoic acid in the reaction while using its derivatives. Sometimes, the functional groups are only operated in an acidic or alkaline medium only (i.e., only in the form of free benzoic acid or only in the form of a salt thereof), and the stability is sufficient. In many cases, an ester such as a methyl ester or an ethyl ester is suitable. Third butyl esters are often effective in sterically protecting carboxyl groups against nucleophiles and are susceptible to cleavage in acidic media (TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, 2nd Edition, John Wiley & Sons, Inc. 1991, p. 227 ff.). Also suitable are groups which are considerably more stable than carboxyl groups, however, they are also readily converted to free carboxylic acids; including, for example, Oxazolines (TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, 2nd Edition, John Wiley & Sons, Inc. 1991, p. 265 ff.; Z. Hell et al., Tetrahedron Letters 43 (2002), 3985-3987) .
各個反應混合物之後續處理通常以已知方法進行，例如利用結晶化、水性萃取處理、層析法或彼等方法之組合。 Subsequent treatment of the individual reaction mixtures is generally carried out by known methods, for example by crystallization, aqueous extraction treatment, chromatography or a combination of these methods.
依照上述反應可合成之大量式(I)化合物及/或其鹽亦可以並行方式製備，其中並行方式可以手動或部分或完全自動化方式進行。於此，得以舉例而言，使反應程序、後續處理或產物或中間體之純化自動化。整體而言，此欲被理解為意指，舉例而言，如D.Tiebes於Combinatorial Chemistry-Synthesis,Analysis,Screening(Editor Günther Jung),Wiley 1999第1至34頁中敘述之程序。 A large amount of the compound of the formula (I) and/or its salt which can be synthesized according to the above reaction can also be produced in a parallel manner, wherein the parallel manner can be carried out manually or partially or completely automatically. Here, for example, the reaction procedure, subsequent processing or purification of the product or intermediate is automated. In general, this is intended to mean, for example, the procedure described in D. Tiebes, Combinatorial Chemistry-Synthesis, Analysis, Screening (Editor Günther Jung), Wiley 1999, pages 1 to 34.
若干市售可得裝置可於並行反應程序及後續處理中使用，例如，Calpyso反應槽得自Barnstead International,Dubuque,Iowa 52004-0797,USA；反應站得自Radleys,Shirehill,Saffron Walden,Essex,CB 11 3AZ,England或MultiPROBE自動化工作站得自Perkin Elmar,Waltham,Massachusetts 02451,USA。尤其是，用於並行純化製備過程中產生的式(I)化合物及其鹽或中間體之色層分析裝置，舉例而言，係得自ISCO,Inc.,4700 Superior Street,Lincoln,NE 68504,USA。 Several commercially available devices can be used in parallel reaction procedures and subsequent processing, for example, the Calpyso reaction tank is available from Barnstead International, Dubuque, Iowa 52004-0797, USA; the reaction station is available from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MultiPROBE automation workstations were obtained from Perkin Elmar, Waltham, Massachusetts 02451, USA. In particular, a chromatography apparatus for use in parallel purification of a compound of formula (I) and a salt or intermediate thereof produced during the preparation, for example, is available from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
所列舉之裝置導向模組化程序，其中個別單次操作(passes)均為自動化，但是單次操作間必須進行手動操作；此可藉由使用部分或完全整合式自動系統而規避，其中相關之自動模組係利用例如機器人來操作。此類自動系統可得自，例如，Caliper,Hopkinton,MA 01748,USA。 The device-oriented modularization program is listed, in which individual single passes are automated, but manual operations must be performed between single operations; this can be circumvented by using a partially or fully integrated automatic system, where relevant The automatic module is operated by, for example, a robot. Such automated systems are available, for example, from Caliper, Hopkinton, MA 01748, USA.
個別、或多個合成步驟之執行可藉助於使用聚合物-支撐之試劑/清除劑樹脂。專業文獻敘述一系列之實驗流程，例如，於ChemFiles,Vol.4,No.1,Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis(Sigma-Aldrich)中。 The individual, or multiple, synthetic steps can be performed by means of a polymer-supported reagent/scavenger resin. The professional literature describes a series of experimental procedures, for example, in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).
除了本文所述方法之外，式(I)化合物及其鹽之製備可完全或部分利用固相支撐法進行。欲達此目的，須使合成或適用於相關程序之合成之個別中間體、或所有中間體與合成樹脂結合。固相支撐之合成方法於專業文獻中充分被敘述；例如，於Barry A.Bunin之“The Combinatorial Index”,Academic Press,1998及Combinatorial Chemistry-Synthesis,Analysis,Screening(Editor Günther Jung),Wiley,1999中。又，使用固相支撐之合成方法容許一系列文獻上已知之實驗流程可手動或以自動化方式進行；例如，該反應可利用IRORI技術，於得自Nexus Biosystems,12140 Community Road,Poway,CA92064,USA之微反應器中進行。 In addition to the methods described herein, the preparation of the compounds of formula (I) and salts thereof can be carried out in whole or in part by solid phase support. To this end, individual intermediates, or all intermediates, which are synthetic or suitable for the synthesis of the relevant procedures, must be combined with synthetic resins. The synthesis of solid support is well described in the professional literature; for example, in "The Combinatorial Index" by Barry A. Bunin, Academic Press, 1998 and Combinatorial Chemistry-Synthesis, Analysis, Screening (Editor Günther Jung), Wiley, 1999 in. Again, synthetic methods using solid support allow a range of experimental procedures known in the literature to be performed manually or in an automated manner; for example, the reaction can be performed using IRORI technology from Nexus Biosystems, 12140 Community Road, Poway, CA 92064, USA. Performed in a microreactor.
於固體以及液相中進行個別或多個合成步驟可借助於使用微波技術；一系列實驗流程見述於專業文獻，例如Microwaves in Organic and Medicinal Chemistry(Editors C.O.Kappe and A.Stadler),Wiley,2005中。 Individual or multiple synthetic steps in solid and liquid phase can be performed by means of microwave technology; a series of experimental procedures are described in specialized literature, such as Microwaves in Organic and Medicinal Chemistry (Editors COKappe and A. Stadler), Wiley, 2005. in.
依照本文所述方法之製備，產生呈物質集合形式之式(I)化合物及其鹽，稱為物質庫；本發明亦係有關含有至少兩種式(I)化合物及其鹽之物質庫。 The preparation of the compounds of formula (I) and their salts in the form of a collection of materials, referred to as a library of materials, in accordance with the methods described herein; the invention is also directed to a library of materials comprising at least two compounds of formula (I) and salts thereof.
根據本發明之式(I)化合物(及/或其鹽)，下文中統稱為"根據本發明之化合物"，具有對抗廣譜之經濟上重要單子葉及雙子葉一年生有害植物之優異除草活性。該等活性物質亦有效地作用於從地下莖、根莖或其他多年生器官產生幼芽且難以控制之多年生有害植物。 The compound (and/or its salt) of the formula (I) according to the present invention, hereinafter collectively referred to as "the compound according to the present invention", has excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual harmful plants. These active substances also act effectively on perennial harmful plants that produce shoots from underground stems, rhizomes or other perennial organs that are difficult to control.
因此，本發明亦有關控制有害植物或調控植物(較佳為作物植物)生長之方法，其中係將根據本發明之一或多種化合物施加於植物(例如單子葉或雙子葉雜草等有害植物或不為所欲之作物植物)、種子(例如榖粒、種子或如塊莖或帶芽幼枝等營養繁殖芽)或植物生長地區(例如栽培區域)。於本說明書中，根據本發明之化合物可於例如種植前(適當時，亦可將其併入土壤中)、萌芽前或萌芽後進行施加。可被根據本發明化合物控制之單子葉及雙子葉雜草植物群之個別代表性實例將被述及，惟不擬對特定物種構成侷限。 Accordingly, the present invention also relates to a method of controlling the growth of a harmful plant or regulating a plant, preferably a crop plant, wherein a compound according to one or more compounds of the present invention is applied to a plant (for example, a harmful plant such as monocotyledon or dicotyledonous weed or Unintentional crop plants), seeds (such as glutinous grains, seeds or vegetative breeding buds such as tubers or young shoots) or plant growing areas (such as cultivated areas). In the present specification, the compound according to the present invention can be applied, for example, before planting (and, if appropriate, in the soil), before or after germination. Individual representative examples of monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds of the present invention will be described, but are not intended to limit specific species.
單子葉有害植物之屬別：山羊草屬(Aegilops)、鵝觀草屬(Agropyron)、小糠草屬(Agrostis)、看麥娘屬(Alopecurus)、阿披拉草屬(Apera)、燕麥屬(Avena)、臂形草屬(Brachiaria)、雀麥屬 (Bromus)、蒺蔾草屬(Cenchrus)、鴨跖草屬(Commelina)、狗牙根屬(Cynodon)、莎草屬(Cyperus)、龍爪茅屬(Dactyloctenium)、馬唐屬(Digitaria)、稗屬(Echinochloa)、荸薺屬(Eleocharis)、穇屬(Eleusine)、畫眉草屬(Eragrostis)、野黍屬(Eriochloa)、羊茅屬(Festuca)、飄拂草屬(Fimbristylis)、異蕊花屬(Heteranthera)、白茅屬(Imperata)、鴨嘴草屬(Ischaemum)、千金子屬(Leptochloa)、黑麥草屬(Lolium)、鴨舌草屬(Monochoria)、黍屬(Panicum)、雀稗屬(Paspalum)、鷸草屬(Phalaris)、梯牧草屬(Phleum)、早熟禾屬(Poa)、羅氏草屬(Rottboellia)、慈菇屬(Sagittaria)、莞屬(Scirpus)、狗尾草屬(Setaria)、蜀黍屬(Sorghum)。 The genus of monocotyledonous harmful plants: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Oats (Avena), Brachiaria, Brome (Bromus), Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Amaranthus (Echinochloa), Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera ), Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, and genus Sorghum).
雙子葉雜草之屬別：麻屬(Abutilon)、莧屬(Amaranthus)、豬草屬(Ambrosia)、蔓錦葵屬(Anoda)、擬母菊屬(Anthemis)、Aphanes、蒿屬(Artemisia)、濱藜屬(Atriplex)、雛菊屬(Bellis)、鬼針屬(Bidens)、薺屬(Capsella)、飛廉屬(Carduus)、決明屬(Cassia)、矢車菊屬(Centaurea)、藜屬(Chenopodium)、薊屬(Cirsium)、旋花屬(Convolvulus)、曼陀羅屬(Datura)、山螞蝗屬(Desmodium)、Emex、糖芥屬(Erysimum)、大戟屬(Euphorbia)、鼬瓣花屬(Galeopsis)、小米菊屬(Galinsoga)、豬殃殃屬(Galium)、芙蓉屬(Hibiscus)、甘薯屬(Ipomoea)、地膚屬(Kochia)、野芝麻屬(Lamium)、獨行菜屬(Lepidium)、母草屬(Lindernia)、母菊屬(Matricaria)、薄荷屬(Mentha)、山靛屬(Mercurialis)、粟米草屬(Mullugo)、勿忘草屬(Myosotis)、罌粟屬(Papaver)、牽牛花屬(Pharbitis)、車前草屬(Plantago)、蓼屬(Polygonum)、馬齒莧屬(Portulaca)、毛茛屬(Ranunculus)、萊菔屬(Raphanus)、葶藶屬 (Rorippa)、水豬母乳屬(Rotala)、酸模屬(Rumex)、豬毛菜屬(Salsola)、黃菀屬(Senecio)、田菁屬(Sesbania)、金午時花屬(Sida)、芥屬(Sinapis)、茄屬(Solanum)、苦苣菜屬(Sonchus)、尖瓣花屬(Sphenoclea)、繁縷屬(Stellaria)、蒲公英屬(Taraxacum)、菥蓂屬(Thlaspi)、椒草屬(Trifolium)、蕁麻屬(Urtica)、婆婆納屬(Veronica)、菫菜屬(Viola)、蒼耳屬(Xanthium)。 The genus of dicotyledon weeds: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium , Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, and Camille ( Galinsoga), Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia , Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago Plantago), Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex (Rumex), Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Chicory (Sonchus), Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica , Viola, Xanthium.
若根據本發明化合物於萌芽前施加於土壤表面，則或者完全抑制雜草幼苗之出現，或者雜草生長至子葉期後停止生長，最後，於三至四週後完全凋萎。 If the compound according to the invention is applied to the surface of the soil prior to germination, the emergence of weed seedlings is completely inhibited, or the weeds are stopped after growth to the cotyledon stage, and finally, completely wilted after three to four weeks.
當活性物質於萌芽後施加於綠色植物部位時，則處理後生長即停止，有害植物保持於施加時之生長期，或於一定時間後完全凋萎，因此對作物植物有害之雜草競爭，可於初期時間點以持續方式排除。 When the active substance is applied to the green plant part after germination, the growth stops after the treatment, the harmful plant remains in the growing period when applied, or completely withered after a certain time, so that the weeds harmful to the crop plants compete. Excluded in a continuous manner at the initial time.
雖然根據本發明之化合物對單子葉及雙子葉雜草展現顯著之除草活性，惟重要經濟作物之作物植物，例如雙子葉作物之花生屬(Arachis)、甜菜屬(Beta)、芸苔屬(Brassica)、香瓜屬(Cucumis)、南瓜屬(Cucurbita)、向日葵屬(Helianthus)、胡蘿蔔屬(Daucus)、大豆屬(Glycine)、棉屬(Gossypium)、甘薯屬、萵苣屬(Lactuca)、亞麻屬(Linum)、番茄屬(Lycopersicon)、煙草屬(Nicotiana)、菜豆屬(Phaseolus)、豌豆屬(Pisum)、茄屬(Solanum)、蠶豆屬(Vicia)，或單子葉作物之蔥屬(Allium)、鳳梨屬(Ananas)、天門冬屬(Asparagus)、燕麥屬、大麥屬(Hordeum)、稻屬(Oryza)、黍屬、甘蔗屬(Saccharum)、黑麥屬(Secale)、蜀黍屬、小黑麥屬(Triticale)、小麥屬(Triticum)、玉米屬(Zea)，特別是玉米及小麥， 則視根據本發明各化合物之結構及其施加率而定，僅具微小程度傷害或完全無傷害；此為本發明化合物高度適用於選擇性控制植物作物(如農業上有用植物或觀賞植物)中不為所欲植物生長之原因。 Although the compounds according to the invention exhibit significant herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of important economic crops, such as Arachis, Beet, and Brassica of the dicotyledonous crops (Brassica) ), Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Sweet Potato, Lactuca, Flax ( Linum), Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or allium of monocotyledon, Ananas, Asparagus, Oats, Hordeum, Oryza, Amaranthus, Saccharum, Secale, Amaranthus, Triticale Triticale, Triticum, Zea, especially corn and wheat, Depending on the structure of the compounds according to the invention and their rate of application, they are only slightly or completely harmless; this is a highly suitable compound for the selective control of plant crops (eg agriculturally useful plants or ornamental plants). Not the reason for the growth of the desired plants.
再者，根據本發明化合物(視其各自結構及施加率而定)於作物植物中具顯著之生長調控性質。彼等以調控方式參與植物代謝，因此可用於以針對性方式影響植物成分，及用於如，舉例而言，經由引發乾燥及遲緩生長而促進收成。此外，彼等亦適用於一般性地控制及抑制不為所欲之營養生長，而於過程中不會破壞植物。於許多單子葉及雙子葉作物中，抑制營養生長扮演重要角色，因為藉此可例如減少或徹底防止倒伏。 Furthermore, the compounds according to the invention (depending on their respective structure and rate of application) have significant growth regulating properties in crop plants. They participate in plant metabolism in a regulated manner and are therefore useful for influencing plant components in a targeted manner and for facilitating harvesting, for example, by initiating dryness and slow growth. In addition, they are also suitable for general control and suppression of undesired vegetative growth without destroying plants during the process. In many monocotyledonous and dicotyledonous crops, inhibition of vegetative growth plays an important role because it can, for example, reduce or completely prevent lodging.
由於其除草及植物生長調控性質，活性物質亦可用於控制基因改造植物或經習知突變誘發改造植物之作物中之有害植物。通常，基因轉殖植物之特點在於特別有利之性質，例如，對特定除害劑(主要為特定除草劑)之抗性、對植物疾病或植物疾病之致病生物(例如特定昆蟲或例如真菌、細菌等微生物或病毒)之抗性；其他特殊性質舉例而言係有關收穫物料之產量、品質、貯藏性、組成及特殊成分。因此，具有增加澱粉含量或經修飾之澱粉品質之基因轉殖植物或收穫物料具有不同脂肪酸組成者為已知。 Due to their herbicidal and plant growth regulating properties, the active substance can also be used to control genetically modified plants or harmful plants in crops that have been modified to induce plants by conventional mutations. In general, genetically transformed plants are characterized by particularly advantageous properties, for example, resistance to specific pesticides (primarily specific herbicides), pathogenic organisms to plant diseases or plant diseases (eg specific insects or eg fungi, Resistance to microorganisms or viruses such as bacteria; other special properties are, for example, the yield, quality, storage, composition and specific ingredients of the harvested material. Therefore, it is known that genetically transformed plants or harvested materials having increased starch content or modified starch quality have different fatty acid compositions.
較佳為使用根據本發明化合物或其鹽於經濟上重要之有用植物及觀賞植物(舉例而言，如小麥、大麥、黑麥、燕麥、高粱與小米、稻米、樹薯與玉米之穀類或者甜菜、棉花、大豆、油菜、馬鈴薯、番茄、豌豆等作物及其他蔬菜類)之基因轉殖作物。較佳為使用根據本發明化合物作為對除草劑之植物毒性作用具抗 性、或已經由基因重組方法使其具抗性之有用植物作物之除草劑用。 It is preferred to use useful plants and ornamental plants which are economically important according to the compound of the present invention or a salt thereof (for example, wheat, barley, rye, oats, sorghum and millet, rice, cassava and corn grains or beets) Genetically modified crops of crops such as cotton, soybeans, canola, potatoes, tomatoes, peas, and other vegetables. It is preferred to use the compound according to the invention as a phytotoxic effect against the herbicide A herbicide for use in a useful plant crop that has been rendered resistant by genetic recombination.
產生與現有植物比較具修飾性質之新穎植物之習知方法為，例如，傳統育種法及變異植株之生成。替代地，具修飾性質之新穎植物可借助基因重組法而產生(參見，例如，EP-A-0221044、EP-A-0131624)。例如，下述已見述於數個案例中：- 以修飾植物中合成之澱粉為目的之作物植物之重組修飾(例如WO 92/11376、WO 92/14827、WO 91/19806)，- 對特定固殺草(glufosinate)型(參見，例如，EP-A-0242236、EP-A-242246)或嘉磷塞(glyphosate)型(WO 92/00377)或磺醯脲型(EP-A-0257993、US-A-5013659)除草劑具抗性之基因轉殖作物植物，- 能產生蘇力菌(Bacillus thuringiensis)毒素(Bt毒素)(其使植物對特定害物具抗性)之基因轉殖作物植物，例如棉花(EP-A-0142924、EP-A-0193259)，- 具修飾脂肪酸組成之基因轉殖作物植物(WO 91/13972)，- 具新穎成分或次級代謝物(例如新穎植物防禦素，其導致增強之疾病抗性)之基因改造作物植物(EPA 309862、EPA0464461)，- 具減少之光呼吸作用，其特徵為產量較高及逆境耐性較強之基因改造作物植物(EPA 0305398)，- 產生醫藥上或診斷上重要的蛋白質之基因轉殖作物植物[分子製藥農場(molecular pharming)"]，- 其特點為產量較高或品質較佳之基因轉殖作物植物， - 其特點為例如上述新穎性質之組合("基因堆疊")之基因轉殖作物植物。 Conventional methods for producing novel plants having modified properties compared to existing plants are, for example, conventional breeding methods and the production of mutant plants. Alternatively, novel plants with modified properties can be produced by means of genetic recombination (see, for example, EP-A-0221044, EP-A-0131624). For example, the following has been described in several cases: - recombinant modifications of crop plants for the purpose of modifying starch synthesized in plants (eg WO 92/11376, WO 92/14827, WO 91/19806), - specific Glufosinate type (see, for example, EP-A-0242236, EP-A-242246) or glyphosate type (WO 92/00377) or sulfonylurea type (EP-A-0257993, US-A-5013659) Herbicide-Resistant Gene-Transplanting Crop Plants - Gene-transgenic crops capable of producing Bacillus thuringiensis toxin (Bt toxin) which confers resistance to specific pests Plants, such as cotton (EP-A-0142924, EP-A-0193259), genetically modified crop plants with modified fatty acid composition (WO 91/13972), with novel components or secondary metabolites (eg novel plant defenses) Genetically modified crop plants (EPA 309862, EPA0464461), which have enhanced disease resistance, have reduced photorespiration and are characterized by high yield and stress tolerance of genetically modified crop plants (EPA 0305398) ,- Gene-generating crop plants that produce medicinal or diagnostically important proteins [Molecular Pharmaceutical Farm (molecula r pharming)"], - a gene-transferred crop plant characterized by higher yield or better quality, - characterized by a gene-transferred crop plant such as the combination of the above novel properties ("gene stacking").
可用以產生具修飾性質之新穎基因轉殖植物之大量分子生物學技術，原則上為已知；參見，例如，I.Potrykus and G.Spangenberg(eds.)Gene Transfer to Plants,Springer Lab Manual(1995),Springer Verlag Berlin,Heidelberg.或Christou,"Trends in P1ant Science" 1(1996)423-431。 A large number of molecular biology techniques that can be used to generate novel gene-transforming plants with modified properties are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995) ), Springer Verlag Berlin, Heidelberg. or Christou, "Trends in P1ant Science" 1 (1996) 423-431.
欲進行此類基因重組操作，可能將核酸分子引入質體中，容許由於DNA序列重組之致突變作用或序列修飾。舉例而言，可進行鹼基置換，移除部分序列，或可借助於標準方法，添加天然或合成序列。為使DNA片段彼此連結，可能添加轉接子(adapters)或連接子(linkers)於諸片段；參見，例如，Sambrook et al.,1989,Molecular Cloning,A Laboratory Manual,2nd ed.,Cold Spring Harbor Laboratory Press,Cold Spring Harbor,NY；或Winnacker "Gene und Klone",VCH Weinheim 2nd ed.,1996。 To perform such a genetic recombination operation, it is possible to introduce a nucleic acid molecule into the plastid, allowing mutagenic or sequence modification due to recombination of the DNA sequence. For example, base substitutions can be made, partial sequences removed, or natural or synthetic sequences can be added by standard methods. In order to link the DNA fragments to each other, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone", VCH Weinheim 2nd ed., 1996.
具有降低基因產物活性的植物細胞之產生可，例如，經由至少一對應反義RNA(為達成共抑制效應之意義RNA)之表現，或經由至少一對應建構核糖核酸酶(其特異地切割上述基因產物之轉錄本)之表現，予以達成。欲進行此操作，首先可能使用包含涵蓋可能存在之任何側翼序列之基因產物所有編碼序列之DNA分子，或者僅包含部分編碼序列(必須夠長而能於細胞中引起反義效應)之DNA分子；亦可能使用與基因產物之編碼序列具高度同源性(惟不完全相同)之DNA序列。 The production of plant cells having reduced gene product activity can, for example, be via at least one corresponding antisense RNA (for the purpose of achieving a cosuppressive effect), or via at least one corresponding construction of a ribonuclease (which specifically cleaves the above gene) The performance of the transcript of the product is achieved. To do this, it is first possible to use a DNA molecule comprising all of the coding sequences of the gene product covering any flanking sequences that may be present, or a DNA molecule comprising only a portion of the coding sequence (which must be long enough to cause an antisense effect in the cell); It is also possible to use DNA sequences that are highly homologous (but not identical) to the coding sequence of the gene product.
於植物中表現核酸分子時，所合成之蛋白質可定位 於植物細胞之任何區間。然而，為了達成於特定區間之定位，可能例如連接編碼區至確保定位於特定區間之DNA序列。此等序列為熟習技藝人士所悉知[參見，例如，Braun et al.,EMBO J.11(1992),3219-3227；Wolter et al.,Proc.Natl.Acad.Sci.USA 85(1988),846-850；Sonnewald et al.,Plant J.1(1991),95-106]。核酸分子亦可於植物細胞之胞器中表現。 When a nucleic acid molecule is expressed in a plant, the synthesized protein can be positioned In any interval of plant cells. However, in order to achieve localization in a particular interval, it is possible, for example, to link the coding region to ensure that the DNA sequence is located in a particular interval. Such sequences are known to those skilled in the art [see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988). , 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106]. Nucleic acid molecules can also be expressed in the organelles of plant cells.
利用已知技術，可使基因轉殖植物細胞再生，得到完整植物。原則上，基因轉殖植物可為任何植物品種之植物，亦即，單子葉及雙子葉植物兩者皆可。 Gene transfer plants can be regenerated using known techniques to obtain whole plants. In principle, the genetically transformed plant can be a plant of any plant species, that is, both monocotyledonous and dicotyledonous plants.
因此，由於同源(=天然)基因或基因序列之過度表現、壓抑或抑制或異源(=外來)基因或基因序列表現之結果，可得到具改造性質特點之基因轉殖植物。 Thus, genetically altered plants characterized by engineered properties can be obtained as a result of overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or heterologous (=foreign) genes or gene sequences.
較佳為於對生長調節劑[如，舉例而言，麥草畏(dicamba)]具抗性、或對抗抑制植物必需酵素[例如，乙醯乳酸合成酶(ALS)、EPSP合成酶、麩胺醯胺合成酶(GS)或羥苯丙酮酸二氧酶(HPPD)]之除草劑、或對抗得自磺醯脲類、嘉磷塞、固殺草或苯甲醯異唑類及類似活性物質組群之除草劑之基因轉殖作物中，使用根據本發明化合物。 Preferably, it is resistant to growth regulators (such as, for example, dicamba), or to anti-inhibition of plant essential enzymes [eg, acetaminolate synthase (ALS), EPSP synthase, glutamine oxime] a herbicide of amine synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD), or against sulfonylureas, carbamazepines, chlorpyrifos or benzamidine In the genetically transgenic crops of the herbicides of the azoles and similar active substance groups, the compounds according to the invention are used.
根據本發明之活性物質用於基因轉殖作物時，除了可於其他作物中觀察到之對有害植物之作用外，經常觀察到特異於應用於討論中基因轉殖作物之作用，例如，可控制之經修飾或具體擴大之雜草譜、可供應用之經修飾之施加率、與基因轉殖作物具抗性的除草劑具相當良好之結合性、及對基因轉殖作物植物生長與產量之影響。 When the active substance according to the present invention is used for genetically transgenic crops, in addition to the effects on harmful plants observed in other crops, the role specific to the genetically-transferred crops in the discussion is often observed, for example, controllable The modified or specifically expanded weed spectrum, the modified application rate applicable for application, the herbicide with resistance to genetically transgenic crops, and the combination of plant growth and yield of genetically transgenic crops influences.
因此，本發明亦有關使用根據本發明化合物作為除草劑，以控制基因轉殖作物植物中之有害植物之用途。 Accordingly, the invention also relates to the use of a compound according to the invention as a herbicide to control the harmful plants in a genetically transgenic crop plant.
根據本發明化合物可呈可濕性粉劑、可乳化濃縮物、噴霧液、粉劑或粒劑形式之習知製劑使用。因此，本發明亦有關包含根據本發明化合物之除草及植物生長調節組成物。 The compounds according to the invention may be used in the form of conventional formulations in the form of wettable powders, emulsifiable concentrates, sprays, powders or granules. Accordingly, the invention also relates to herbicidal and plant growth regulating compositions comprising a compound according to the invention.
根據本發明化合物視主要生物及/或物理化學參數而定，可以各種方式調配。可能之調配物實例為：可濕性粉劑(WP)、水溶性粉劑(SP)、水溶性濃縮物、可乳化濃縮物(EC)、乳液(EW)(例如水包油型及油包水型乳液)、噴霧液、懸浮濃縮物(SC)、油性或水性分散液、油溶性溶液、膠囊懸浮液(CS)、粉劑(DP)、種子拌藥產物、供散播施加於土壤之粒劑、微粒型粒劑(GR)、噴霧粒劑、包衣粒劑與吸附粒劑、水可分散粒劑(WG)、水溶性粒劑(SG)、ULV調配物、微膠囊及蠟。 The compounds according to the invention depend on the main biological and/or physicochemical parameters and can be formulated in a variety of ways. Examples of possible formulations are: wettable powders (WP), water soluble powders (SP), water soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) (eg oil-in-water and water-in-oil) Emulsion), spray liquid, suspension concentrate (SC), oily or aqueous dispersion, oil-soluble solution, capsule suspension (CS), powder (DP), seed mixed product, granules for application to soil, particles Granules (GR), spray granules, coated granules and adsorbent granules, water dispersible granules (WG), water soluble granules (SG), ULV formulations, microcapsules and waxes.
彼等調配物個別類型原則上為已知，及見述於，例如：Winnacker-Küchler,"Chemische Technologie"[化學技術],volume 7,C.Hanser Verlag Munich,4th Ed.1986；Wade van Valkenburg,"Pesticide Formulations",Marcel Dekker,N.Y.,1973；K.Martens,"Spray Drying" Handbook,3rd Ed.1979,G.Goodwin Ltd.London。 The individual types of their formulations are known in principle and are described, for example, in Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], volume 7, C. Hanser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
所需之調配助劑(例如惰性材料、界面活性劑、溶劑及進一步之添加劑)亦為已知，及見述於，例如：Watkins,"Handbook of Insecticide Dust Diluents and Carriers",2nd Ed.,Darland Books,Caldwell N.J.,H.v.Olphen,"Introduction to Clay Colloid Chemistry"；2nd Ed.,J.Wiley & Sons,N.Y.；C.Marsden,"Solvents Guide"；2nd Ed.,Interscience,N.Y.1963；McCutcheon's "Detergents and Emulsifiers Annual",MC Publ.Corp.,Ridgewood N.J.；Sisley and Wood,"Encyclopedia of Surface Active Agents",Chem.Publ.Co.Inc.,N.Y.1964；Schönfeldt,"Grenzflächenaktive Äthylenoxidaddukte"[界面活性環氧乙烷加合物],Wiss.Verlagsgesell.,Stuttgart 1976；Winnacker-Küchler,"Chemische Technologie"[化學技術]，volume 7,C.Hanser Verlag Munich,4th Ed.1986。 The desired formulation aids (e.g., inert materials, surfactants, solvents, and further additives) are also known, and are described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland. Books, Caldwell NJ, HvOlphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt , "Grenzflächenaktive Äthylenoxidaddukte" [Interfacial Active Ethylene Oxide Adduct], Wiss.Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.
以彼等調配物為基礎，亦可能製備與其他殺蟲活性物質(例如，舉例而言，殺昆蟲劑、殺蟎劑、除草劑、殺真菌劑)、及與防護劑、肥料及/或生長調節劑之組合物(例如呈預拌或桶混形式)。適當防護劑(safener)為，例如，吡唑解草酯(mefenpyr-diethyl)、環丙磺醯胺、雙苯唑酸(isoxadifen-ethyl)、解毒喹(cloquintocet-mexyl)與二氯丙烯胺(dichlormid)。 Based on their formulations, it is also possible to prepare with other insecticidal active substances (for example, insecticides, acaricides, herbicides, fungicides), and with protective agents, fertilizers and/or growth. A composition of the conditioning agent (for example in the form of a premixed or tank mix). Suitable safeners are, for example, mefenpyr-diethyl, cyproterone, diphenyl Isoxadifen-ethyl, cloquintocet-mexyl and dichlormid.
可濕性粉劑為可均勻分散於水中之製劑，其除了活性物質外，亦包含離子性及/或非離子性界面活性劑(潤濕劑、分散劑)，例如，聚氧乙烯化之烷基酚類、聚氧乙烯化之脂肪醇類、聚氧乙烯化之脂肪胺類、脂肪醇聚乙二醇醚硫酸鹽、鏈烷磺酸鹽、烷基苯磺酸鹽、木質素磺酸鈉、2,2'-二萘甲烷-6,6'-二磺酸鈉、二丁基萘磺酸鈉或者油醯甲基牛磺酸鈉，以及稀釋劑或惰性物質。製備可濕性粉劑時，係將具除草活性之物質，舉例而言，於習知裝置(例如錘式研磨機、風箱式研磨機及空氣噴射式研磨機)中精細研磨，同時或隨後與調配助劑混合。 The wettable powder is a preparation which can be uniformly dispersed in water, and contains, in addition to the active material, an ionic and/or nonionic surfactant (wetting agent, dispersing agent), for example, a polyoxyethylated alkyl group. Phenolic, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates, alkylbenzene sulfonates, sodium lignosulfonate, 2,2'-Naphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium sulfonate methyl taurate, and a diluent or inert substance. In the preparation of a wettable powder, the herbicidal active material is, for example, finely ground in a conventional device such as a hammer mill, a bellows mill and an air jet mill, simultaneously or subsequently with Mixing additives.
可乳化濃縮物之製備係使活性物質溶於有機溶劑， 例如丁醇、環己酮、二甲基甲醯胺、二甲苯或較高沸點芳烴或碳氫化合物或添加一或多種離子性及/或非離子性界面活性劑(乳化劑)之有機溶劑混合物中。可使用之乳化劑實例為：烷芳基磺酸鈣類(如十二烷基苯磺酸鈣)、或非離子性乳化劑例如脂肪酸聚乙二醇酯類、烷芳基聚乙二醇醚類、脂肪醇聚乙二醇醚類、環氧丙烷/環氧乙烷縮合物、烷基聚醚類、山梨醇酐酯類例如，舉例而言，山梨醇酐脂肪酸酯類或聚氧乙烯山梨醇酐酯類例如，舉例而言，聚氧乙烯山梨醇酐脂肪酸酯類。 The emulsifiable concentrate is prepared by dissolving the active substance in an organic solvent. For example, butanol, cyclohexanone, dimethylformamide, xylene or a higher boiling aromatic hydrocarbon or hydrocarbon or an organic solvent mixture with one or more ionic and/or nonionic surfactants (emulsifiers) in. Examples of emulsifiers that can be used are: calcium alkaryl sulfonates (such as calcium dodecylbenzene sulfonate), or nonionic emulsifiers such as fatty acid polyethylene glycol esters, alkylaryl polyglycol ethers. Classes, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters, for example, sorbitan fatty acid esters or polyoxyethylene sorbes The alcohol anhydride esters are, for example, polyoxyethylene sorbitan fatty acid esters.
粉劑係使活性物質與細碎之固體物料例如，舉例而言，滑石、天然黏土例如高嶺土、膨土與葉蠟石、或矽藻土一起研磨製得。 The powder is obtained by grinding the active material with finely divided solid materials such as, for example, talc, natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
懸浮濃縮物可為水性或油性；舉例而言，可使用市售可得之珠磨機以濕式研磨法製備，若適當，則可添加如其他調配物類型情形下已如上列舉為實例之界面活性劑。 The suspension concentrate may be aqueous or oily; for example, it may be prepared by wet milling using a commercially available bead mill, and if appropriate, an interface as exemplified above, as in the case of other formulation types may be added. Active agent.
乳液，例如水包油型乳液(EW)，舉例而言，可使用水性有機溶劑與，若適當之如其他調配物類型中已述及為實例之界面活性劑，利用例如攪拌器、膠體研磨機及/或靜態混合器製備。 An emulsion, for example an oil-in-water emulsion (EW), for example, an aqueous organic solvent and, if appropriate, a surfactant as exemplified in other formulation types, for example using a stirrer or a colloid mill And / or static mixer preparation.
粒劑可利用噴塗活性物質於吸附性、顆粒狀之惰性物料上，或借助於黏著劑(例如聚乙烯醇、聚丙烯酸鈉或者礦物油)，將活性物質濃縮物施敷於載劑例(如沙、高嶺石或粒狀惰性物料)表面予以製備。若需要呈與肥料之混合物，則亦可以習知之肥料粒劑生產方式，將適當活性物質顆粒化。 The granules can be applied to the carrier by using the spray active material on an adsorbent, granular inert material, or by means of an adhesive (for example polyvinyl alcohol, sodium polyacrylate or mineral oil). The surface of sand, kaolinite or granular inert material is prepared. If it is desired to present a mixture with the fertilizer, it is also possible to granulate a suitable active substance by means of a conventional method of producing a fertilizer granule.
水可分散粒劑通常可利用習知方法例如噴霧乾燥、流動床造粒、圓盤造粒，以高速攪拌器混合，無固態惰性物料下 進行擠壓，予以製備。 The water-dispersible granules can usually be mixed by a conventional method such as spray drying, fluidized bed granulation, disk granulation, and mixed with a high-speed agitator without solid inert material. It is extruded and prepared.
圓盤粒劑、流動床粒劑、擠壓粒劑及噴霧粒劑之製備，參見，例如，見述於"Spray-Drying Handbook" 3rd ed.1979,G.Goodwin Ltd.,London；J.E.Browning,"Agglomeration",Chemical and Engineering 1967,pages 147 et seq.；"Perry's Chemical Engineer's Handbook",5th Ed.,McGraw-Hill,New York 1973,p.8-57中之方法。 For the preparation of disc granules, flowing bed granules, extruded granules and spray granules, see, for example, see "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JEBrowning, "Agglomeration", Chemical and Engineering 1967, pages 147 et seq.; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, p. 8-57.
關於調配作物保護產物之進一步細節，參見，例如，G.C.Klingman,"Weed Control as a Science",John Wiley and Sons,Inc.,New York,1961,pages 81-96與J.D.Freyer,S.A.Evans,"Weed Control Handbook",5th Ed.,Blackwell Scientific Publications,Oxford,1968,pages 101-103。 For further details on blending crop protection products, see, for example, GCKlingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JDFreyer, SAEvans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
通常，農業化學製劑包含0.1至99重量%，特別是0.1至95重量%之根據本發明化合物。可濕性粉劑中，活性物質濃度為，例如，約10至90重量%，至100重量%之差額量由習知調配物成分組成。可乳化濃縮物之情形下，活性物質濃度可達約1至90，較佳為5至80重量%。粉劑型調配物包含1至30重量%活性物質，於多數情形下較佳為5至20重量%活性物質；噴霧液包含約0.05至80，較佳為2至50重量%活性物質。水可分散粒劑之情形下，活性物質含量部分視該活性化合物係呈液體或者固體形式，及使用中之粒化助劑、填充劑等而定。例如，於水可分散粒劑情形下，活性物質含量係介於1與95重量%間，較佳為介於10與80重量%間。 In general, the agrochemical preparations comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of the compound according to the invention. In the wettable powder, the active substance concentration is, for example, about 10 to 90% by weight, and the difference of 100% by weight is composed of a conventional formulation component. In the case of an emulsifiable concentrate, the active substance may have a concentration of from about 1 to 90, preferably from 5 to 80% by weight. The powder formulation comprises from 1 to 30% by weight of active substance, in most cases preferably from 5 to 20% by weight of active substance; the spray liquid comprises from about 0.05 to 80, preferably from 2 to 50% by weight of active substance. In the case of water-dispersible granules, the active substance content depends, in part, on the active compound in liquid or solid form, and in the use of granulation aids, fillers and the like. For example, in the case of water dispersible granules, the active substance content is between 1 and 95% by weight, preferably between 10 and 80% by weight.
此外，所述活性物質調配物，若適當，則於各情形 下包含習知助劑，例如黏著劑、潤濕劑、分散劑、乳化劑、滲透劑、防腐劑、防凍劑、溶劑、填充劑、載劑、著色劑、消泡劑、蒸發抑制劑、及pH與黏度調節劑。 In addition, the active substance formulation, if appropriate, is in each case Containing conventional auxiliaries such as adhesives, wetting agents, dispersing agents, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoaming agents, evaporation inhibitors, and pH and viscosity modifier.
以彼等調配物為基礎，亦可能製備與其他殺蟲活性物質(例如，舉例而言，殺昆蟲劑、殺蟎劑、除草劑、殺真菌劑)、及與防護劑、肥料及/或生長調節劑之組合物(例如呈預拌或桶混形式)。 Based on their formulations, it is also possible to prepare with other insecticidal active substances (for example, insecticides, acaricides, herbicides, fungicides), and with protective agents, fertilizers and/or growth. A composition of the conditioning agent (for example in the form of a premixed or tank mix).
可用於與根據本發明化合物呈混合調配物或呈桶混組合之活性物質為，例如，係基於抑制，舉例而言，見述於例如Weed Research 26(1986)441-445或"The Pesticide Manual",14th edition,The British Crop Protection Council and the Royal Soc.of Chemistry,2003及其中所引用文獻之乙醯乳酸合成酶、乙醯基-CoA羧酶、纖維素合成酶、烯醇式丙酮酸莽草酸-3-磷酸合成酶、麩胺醯胺合成酶、對羥苯丙酮酸二氧酶、八氫茄紅素脫飽和酶、光系統I、光系統II、原紫質元氧化酶之已知活性物質。 Active substances which can be used in combination with the compounds according to the invention in a mixed formulation or in a tank mix are, for example, based on inhibition, for example as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual". , 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and the literature cited therein, acetaminolate synthase, acetyl-CoA carboxylase, cellulose synthase, enol pyruvic acid Known activity of 3-phosphate synthase, glutamine indole synthase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, proto-purpurin oxidase substance.
供使用時，若適當，則將呈市售可得形式出現之調配物以習知方法稀釋，例如於可濕性粉劑、可乳化濃縮物、分散液與水可分散粒劑之情形下，使用水。呈粉劑、土壤顆粒、散播用粒劑、及噴霧液形式之製劑，使用之前通常不以另外之惰性物質進一步稀釋。 When used, if appropriate, the formulations which are present in commercially available form are diluted by conventional methods, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules, water. Formulations in the form of powders, soil granules, granules for dispersion, and sprays are usually not further diluted with additional inert materials prior to use.
式(I)化合物所需施加率係以外部條件(例如溫度、濕度、所使用除草劑之性質等)為函數而不同；其可於寬廣界限內變化，例如介於0.001與1.0公斤/公頃間及更多之活性物質，惟較佳為介於0.005與750公克/公頃間。 The desired rate of application of the compound of formula (I) varies as a function of external conditions (eg temperature, humidity, nature of the herbicide used, etc.); it can vary within wide limits, for example between 0.001 and 1.0 kg/ha And more active substances, preferably between 0.005 and 750 g/ha.
茲利用下述實例說明本發明。 The invention is illustrated by the following examples.
3-(N-氰基-S-甲基亞磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺(表實例編號10-160)及3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺(表實例編號1-160)之合成 3-(N-Cyano-S-methylsulfoximineimine)-2-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoro Methyl)benzamide (Table Example No. 10-160) and 3-(N-cyano-S-methylsulfonimide)-methoxy-N-(1-methyl- Synthesis of 1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide (Table Example No. 1-160)
步驟1：2-甲氧基-3-(甲硫基)-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺之合成 Step 1: Synthesis of 2-methoxy-3-(methylthio)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide
添加1.45克(98重量%；14.3毫莫耳)5-胺基-1-甲基-1H-四唑至3.00克(11.3毫莫耳)2-甲氧基-3-(甲硫基)-4-(三氟甲基)苯甲酸之30毫升無水吡啶溶液中。然後添加2.00克(15.8毫莫耳)草醯氯，接著於室溫(RT)攪拌此混合物三天。然後添加另外500毫克(3.94毫莫耳)草醯氯，接著於RT攪拌此混合物16小時。後續處理係於旋轉蒸發器上使內容物實質上不含溶劑；殘留物與二氯甲烷及碳酸氫鈉飽和溶液一起攪拌；然後分離有機相，於旋轉蒸發器去除其溶劑；以層析法純化殘留物，得到1.83克乾淨產物。 Add 1.45 g (98 wt%; 14.3 mmol) 5-amino-1-methyl-1H-tetrazole to 3.00 g (11.3 mmol) 2-methoxy-3-(methylthio)- 4-(Trifluoromethyl)benzoic acid in 30 ml of anhydrous pyridine solution. Then 2.00 g (15.8 mmol) of chlorophyll chloride was added, followed by stirring the mixture at room temperature (RT) for three days. An additional 500 mg (3.94 mmol) of oxaloquinone chloride was then added, followed by stirring the mixture for 16 hours at RT. The subsequent treatment is carried out on a rotary evaporator so that the contents are substantially free of solvent; the residue is stirred with a saturated solution of dichloromethane and sodium hydrogencarbonate; then the organic phase is separated and the solvent is removed on a rotary evaporator; purification by chromatography The residue gave 1.83 g of a clean product.
步驟2：3-(N-氰基-S-甲基亞磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺及3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺之合成 Step 2: 3-(N-Cyano-S-methylsulfoximineimine)-2-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-4- (Trifluoromethyl)benzamide and 3-(N-cyano-S-methylsulfonimide)-2-methoxy-N-(1-methyl-1H-tetrazole- Synthesis of 5-yl)-4-(trifluoromethyl)benzamide
於RT，相繼添加234毫克(5.56毫莫耳)氰胺與1.06 克(5.96毫莫耳)N-溴琥珀醯亞胺至1.14克(3.27毫莫耳)2-甲氧基-3-(甲硫基)-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺與440毫克(3.92毫莫耳)第三丁醇鉀之70毫升甲醇溶液中。然後於RT攪拌內容物16小時。後續處理係在最多30℃下，於旋轉蒸發器上使混合物不含溶劑；殘留物於150毫升冰冷二氯甲烷與50毫升冰冷10重量%強度硫酸氫鈉水溶液之混合物中攪拌約兩分鐘；進行相分離後，水相以50毫升二氯甲烷萃取；合併之有機相於旋轉蒸發器上去除溶劑；使殘留物混於60毫升乙腈與60毫升水中。然後添加1.57克(9.80毫莫耳)過錳酸鈉一水合物；於RT攪拌反應混合物四天。後續處理係添加10重量%強度硫酸氫鈉水溶液；接著添加水，此混合物以二氯甲烷萃取三次；溫度最多30℃下，使合併之有機相於旋轉蒸發器上去除溶劑；以層析法純化殘留物，得到40毫克3-(N-氰基-S-甲基亞磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺及650毫克3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺。 At RT, add 234 mg (5.56 mmol) of cyanamide to 1.06. 克(5.96 mmol) N-bromosuccinimide to 1.14 g (3.27 mmol) 2-methoxy-3-(methylthio)-N-(1-methyl-1H-tetrazole- 5-Methyl)-4-(trifluoromethyl)benzamide was combined with 440 mg (3.92 mmol) of potassium t-butoxide in 70 mL of methanol. The contents were then stirred at RT for 16 hours. The subsequent treatment is carried out at a maximum of 30 ° C, the mixture is free of solvent on a rotary evaporator; the residue is stirred in a mixture of 150 ml of ice-cold dichloromethane and 50 ml of ice-cold 10% by weight strength aqueous sodium hydrogensulfate solution for about two minutes; After phase separation, the aqueous phase was extracted with 50 mL of dichloromethane; the combined organic phases were evaporated on a rotary evaporator; and the residue was taken from 60 ml of acetonitrile and 60 ml of water. Then 1.57 g (9.80 mmol) of sodium permanganate monohydrate was added; the reaction mixture was stirred at RT for four days. The subsequent treatment is carried out by adding 10% by weight of an aqueous solution of strong sodium hydrogensulfate; then adding water, the mixture is extracted three times with dichloromethane; the combined organic phase is removed on a rotary evaporator at a temperature of up to 30 ° C; purification by chromatography The residue gave 40 mg of 3-(N-cyano-S-methylsulfoximineimine)-2-methoxy-N-(1-methyl-1H-tetrazol-5-yl) -4-(Trifluoromethyl)benzamide and 650 mg of 3-(N-cyano-S-methylsulfonimide)-2-methoxy-N-(1-methyl- 1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.
2-甲氧基-N-(1-甲基-1H-四唑-5-基)-3-[S-甲基-N-(三氟乙醯基)磺醯亞胺醯基]-4-(三氟甲基)苯甲醯胺(表實例編號1-292)之合成 2-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-3-[S-methyl-N-(trifluoroethyl)sulfonimide fluorenyl]-4 Synthesis of -(trifluoromethyl)benzamide (Table Example No. 1-292)
最初裝填100毫克(0.248毫莫耳)3-(N-氰基-S-甲基亞磺醯亞胺醯基)-2-甲氧基-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺於10毫升無水二氯甲烷中，於冰浴中冷卻。添加156毫克(0.744毫莫耳)三氟乙酸酐，1.5小時後，使內容物解凍至RT。於RT攪拌混合物16小時，然後將其傾入至水中，供後續處理用。 內容物以二氯甲烷萃取兩次，進行相分離後，接著於溫度最多30℃下，使混合物於旋轉蒸發器上去除溶劑；以層析法純化殘留物，得到17毫克產物。 Initially filled with 100 mg (0.248 mmol) of 3-(N-cyano-S-methylsulfoximineimine)-2-methoxy-N-(1-methyl-1H-tetrazole- 5-Methyl)-4-(trifluoromethyl)benzamide was cooled in 10 mL of dry dichloromethane in EtOAc. 156 mg (0.744 mmol) of trifluoroacetic anhydride was added and after 1.5 hours the contents were thawed to RT. The mixture was stirred at RT for 16 hours and then poured into water for subsequent processing. The contents were extracted twice with dichloromethane, and after phase separation, the mixture was removed on a rotary evaporator at a temperature of up to 30 ° C; the residue was purified by chromatography to afford 17 mg of product.
2-甲氧基-3-(S-甲基磺醯亞胺醯基)-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲醯胺(表實例編號1-28)之合成 2-methoxy-3-(S-methylsulfonimide)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide Synthesis of amines (Table Example No. 1-28)
添加31.5毫克(0.228毫莫耳)碳酸鉀至36.0毫克(0.076毫莫耳)2-甲氧基-N-(1-甲基-1H-四唑-5-基)-3-[S-甲基-N-(三氟乙醯基)磺醯亞胺醯基]-4-(三氟甲基)苯甲醯胺之5毫升甲醇溶液中；於RT攪拌混合物30分鐘。後續處理係在溫度最多30℃下，於旋轉蒸發器上去除溶劑；使殘留物混於水中，此混合物以二氯甲烷萃取；然後添加一滴冰乙酸於水相，此混合物以二氯甲烷萃取兩次；然後在溫度最多30℃下，於旋轉蒸發器上使水相不含溶劑；殘留物以二氯甲烷攪拌，然後與上述分離之有機相結合；於旋轉蒸發器上去除溶劑，分離出呈殘留物之20毫克產物。 Add 31.5 mg (0.228 mmol) potassium carbonate to 36.0 mg (0.076 mmol) 2-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-3-[S-A A solution of benzyl-N-(trifluoroethyl)sulfonimide fluorenyl]-4-(trifluoromethyl)benzamide in 5 ml of MeOH; The subsequent treatment is carried out at a temperature of up to 30 ° C, the solvent is removed on a rotary evaporator; the residue is mixed in water, the mixture is extracted with dichloromethane; then a drop of glacial acetic acid is added to the aqueous phase, and the mixture is extracted with dichloromethane. Then; at a temperature of up to 30 ° C, the aqueous phase is free of solvent on a rotary evaporator; the residue is stirred with dichloromethane and then combined with the above separated organic phase; the solvent is removed on a rotary evaporator and separated 20 mg of product of the residue.
3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-N-(5-甲基-1,3,4-二唑-2-基)-4-(三氟甲基)苯甲醯胺(表實例編號7-160)之合成 3-(N-Cyano-S-methylsulfonimide fluorenyl)-2-methoxy-N-(5-methyl-1,3,4- Synthesis of oxazol-2-yl)-4-(trifluoromethyl)benzamide (Table Example No. 7-160)
步驟1：3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-4-(三氟甲基)苯甲酸之合成 Step 1: Synthesis of 3-(N-cyano-S-methylsulfonimidoindolyl)-2-methoxy-4-(trifluoromethyl)benzoic acid
添加3.71克(33.1毫莫耳)第三丁醇鉀至4.00克(15.0毫莫耳)2-甲氧基-3-(甲硫基)-4-(三氟甲基)苯甲酸之250毫升甲醇溶液中。攪拌此混合物10分鐘，接著相繼添加1.07克(25.5毫莫耳)氰胺及4.81克(27.0毫莫耳)N-溴琥珀醯亞胺；於RT攪拌內容物2小時。然後於旋轉蒸發器上使混合物不含溶劑，使殘留物混 於各為120毫升乙腈與水之混合物中。添加7.21克(45.1毫莫耳)過錳酸鈉一水合物，於RT攪拌此混合物一週；其間，於一天後及其後一天，各添加3.6克(22.5毫莫耳)過錳酸鈉一水合物。後續處理係添加10重量%強度硫酸氫鈉溶液；於旋轉蒸發器上，溫度最多30℃下，實質上去除溶劑；於冰浴中冷卻殘留物，然後以1M鹽酸酸化；此混合物以冰冷二氯甲烷萃取三次；於旋轉蒸發器上使合併之有機相不含溶劑，以層析法純化殘留物，得到純度80重量%之1.30克產物。 Add 3.71 g (33.1 mmol) potassium t-butoxide to 4.00 g (15.0 mmol) 250 mg of 2-methoxy-3-(methylthio)-4-(trifluoromethyl)benzoic acid In methanol solution. The mixture was stirred for 10 minutes, followed by the sequential addition of 1.07 g (25.5 mmol) of cyanamide and 4.81 g (27.0 mmol) of N-bromosuccinimide; the contents were stirred at RT for 2 hours. The mixture is then freed of solvent on a rotary evaporator to mix the residue. Each was a mixture of 120 ml of acetonitrile and water. 7.21 g (45.1 mmol) of sodium permanganate monohydrate was added, and the mixture was stirred at RT for one week; during the day, one day later and one day later, 3.6 g (22.5 mmol) of sodium permanganate monohydrate was added. Things. The subsequent treatment was carried out by adding 10% by weight of a strong solution of sodium hydrogensulfate; on a rotary evaporator, the solvent was substantially removed at a temperature of up to 30 ° C; the residue was cooled in an ice bath and then acidified with 1 M hydrochloric acid; the mixture was ice-cold dichloro The methane was extracted three times; the combined organic phase was freed of solvent on a rotary evaporator, and the residue was purified by chromatography to yield a product of <RTIgt;
步驟2：3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-N-(5-甲基-1,3,4-二唑-2-基)-4-(三氟甲基)苯甲醯胺之合成 Step 2: 3-(N-Cyano-S-methylsulfonimide fluorenyl)-2-methoxy-N-(5-methyl-1,3,4- Synthesis of oxazol-2-yl)-4-(trifluoromethyl)benzamide
最初裝填350毫克(80重量%；0.869毫莫耳)3-(N-氰基-S-甲基磺醯亞胺醯基)-2-甲氧基-4-(三氟甲基)苯甲酸與151毫克(1.52毫莫耳)2-胺基-5-甲基-1,3,4-二唑於10毫升無水吡啶中，於冰浴中冷卻。添加207毫克(1.63毫莫耳)草醯氯，30分鐘後，使混合物解凍至RT。於RT攪拌內容物2小時，接著添加另外51.8毫克(0.408毫莫耳)草醯氯；然後於RT攪拌此混合物16小時。後續處理時，於旋轉蒸發器上使內容物不含溶劑，使殘留物混於水及二氯甲烷中；經相分離後，於旋轉蒸發器上使有機相不含溶劑，中性條件下，以層析法純化殘留物，得到9.80毫克產物。 Initially charged 350 mg (80% by weight; 0.869 mmol) of 3-(N-cyano-S-methylsulfonimidoindolyl)-2-methoxy-4-(trifluoromethyl)benzoic acid With 151 mg (1.52 mmol) 2-amino-5-methyl-1,3,4- The oxadiazole was cooled in an ice bath in 10 ml of anhydrous pyridine. 207 mg (1.63 mmol) of grass mash was added and after 30 minutes the mixture was thawed to RT. The contents were stirred at RT for 2 hours, followed by the addition of an additional 51.8 mg (0.408 mmol) of chloroform; the mixture was then stirred at RT for 16 hours. In the subsequent treatment, the content is free of solvent on the rotary evaporator, and the residue is mixed in water and dichloromethane; after phase separation, the organic phase is free of solvent on a rotary evaporator under neutral conditions. The residue was purified by chromatography to give 9.
下文表中列出之實例係類似於上述方法予以製備或類似於上述方法製得；彼等化合物為非常特佳者。 The examples listed in the table below were prepared analogously to the methods described above or similar to those described above; their compounds are very particular.
所用縮寫為：Et=乙基 Me=甲基 n-Pr=正丙基 i-Pr=異丙基 The abbreviations used are: Et = ethyl Me = methyl n-Pr = n-propyl i-Pr = isopropyl
c-Pr=環丙基 Ph=苯基 c-Pr=cyclopropyl Ph=phenyl
a)粉劑係使10重量份式(I)化合物及/或其鹽與90重量份滑石(為惰性物質)混合，於錘式研磨機中研細此混合物製得。 a) A powder is prepared by mixing 10 parts by weight of the compound of the formula (I) and/or its salt with 90 parts by weight of talc (inert matter) and grinding the mixture in a hammer mill.
b)易於水中分散之可濕性粉劑係使25重量份式(I)化合物及/或其鹽、64重量份含高嶺土石英(為惰性物質)、10重量份木質素磺酸鉀與1重量份油醯甲基牛磺酸鈉(為潤濕劑及分散劑)混合，於固定之圓盤研磨機(pinned-disk mill)中研磨此混合物製得。 b) a wettable powder which is easily dispersible in water, such that 25 parts by weight of the compound of the formula (I) and/or its salt, 64 parts by weight of kaolinite containing quartz (inert matter), 10 parts by weight of potassium ligninsulfonate and 1 part by weight The mixture of sodium methyl taurate (which is a wetting agent and a dispersing agent) is prepared by grinding the mixture in a pinned-disk mill.
c)易於水中分散之分散濃縮物係使20重量份式(I)化合物及/或其鹽與6重量份烷基酚聚乙二醇醚(®Triton X 207)、3重量份異十三醇聚乙二醇醚(8 EO)與71重量份石蠟系礦物油(沸騰範圍例如約255至達277℃以上)混合，並於碗形研磨機中研磨此混合物至細度低於5微米製得。 c) a dispersion concentrate which is easily dispersible in water is 20 parts by weight of the compound of the formula (I) and/or its salt with 6 parts by weight of an alkylphenol polyglycol ether (® Triton X 207), 3 parts by weight of isotridecyl alcohol Polyethylene glycol ether (8 EO) is mixed with 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to 277 ° C or higher), and the mixture is ground to a fineness of less than 5 μm in a bowl grinder. .
d)可乳化濃縮物係以15重量份式(I)化合物及/或其鹽、75重量份環己酮(為溶劑)與10重量份乙氧基化之壬基酚(為乳化劑)製得。 d) the emulsifiable concentrate is made up of 15 parts by weight of the compound of the formula (I) and/or its salt, 75 parts by weight of cyclohexanone (as a solvent) and 10 parts by weight of an ethoxylated nonylphenol (as an emulsifier). Got it.
e)水可分散粒劑係使75重量份式(I)化合物及/或其鹽、10重量份木質素磺酸鈣、 5重量份月桂基硫酸鈉、3重量份聚乙烯醇與7重量份高嶺土混合，於固定之圓盤研磨機中研磨此混合物，於流動床中利用噴灑於水(造粒液體)上，使粉末粒化而製得。 e) a water-dispersible granule such that 75 parts by weight of the compound of the formula (I) and/or its salt, 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin were mixed, and the mixture was ground in a fixed disc grinder and sprayed on water (granulation liquid) in a fluidized bed to make a powder. Made by granulation.
f)水可分散粒劑亦可於膠體研磨機中，經由均質化及預先粉碎25重量份式(I)化合物及/或其鹽、5重量份2,2'-二萘甲烷-6,6'-二磺酸鈉、2重量份油醯甲基牛磺酸鈉、1重量份聚乙烯醇、17重量份碳酸鈣與50重量份水，接著於珠磨機中研磨此混合物，於噴霧塔中利用單一物質噴嘴噴霧及乾燥所得懸浮液而製得。 f) water-dispersible granules may also be homogenized and pre-pulverized in a colloid mill by 25 parts by weight of a compound of the formula (I) and/or a salt thereof, and 5 parts by weight of 2,2'-dimethylnaphthalene-6,6. '-Sodium disulfonate, 2 parts by weight of sodium sulphate methyl taurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water, followed by grinding the mixture in a bead mill at a spray tower It is prepared by spraying and drying the obtained suspension with a single substance nozzle.
將單子葉或雙子葉雜草或作物植物之種子置於木纖維盆之砂質壤土中，並以土壤覆蓋。然後將調配成可濕性粉劑(WP)或乳化濃縮物(EC)形式之根據本發明之化合物，呈水性懸浮液或乳液形式，以600至800公升/公頃(轉換)之水(添加0.2%潤濕劑)施加率，施加於覆蓋土壤表面。處理後，將盆放置於溫室中，並保持於測試植物之良好生長條件下。經過3週實驗期後，與未經處理之對照組比較，針對測試植物之損傷進行視覺評分[除草活性百分比(%)：100%活性=植物已死，0%活性=類似對照組植物]。 於此，舉例而言，於320公克/公頃之施加率下，化合物編號1-028、1-138及1-270顯示各具至少80%強度之對抗苘麻(Abutilon theophrasti)、反枝莧(Amaranthus retroflexus)、水莎草(Cyperus serotinus)、稗草(Echinochloa crus galli)、母菊(Matricaria inodora)、狗尾草(Setaria viridis)、繁縷(Stellaria media)、婆婆納(Veronica persica)與三色菫(Viola tricolor)之活性。 Seeds of monocotyledonous or dicotyledonous weeds or crop plants are placed in sandy loam of wood fiber pots and covered with soil. The compound according to the invention in the form of a wettable powder (WP) or an emulsified concentrate (EC) is then formulated as an aqueous suspension or emulsion in an amount of from 600 to 800 liters per hectare (converted) of water (0.2% added) Wetting agent) applied rate applied to cover the surface of the soil. After treatment, the pots were placed in a greenhouse and kept under good growth conditions of the test plants. After a 3-week experimental period, the lesions of the test plants were visually scored as compared to the untreated control group [% herbicidal activity (%): 100% activity = plant dead, 0% activity = similar control plants]. Here, for example, at an application rate of 320 g/ha, compound numbers 1-028, 1-138, and 1-270 show at least 80% strength against ramie ( Abutilon theophrasti ), anti-branches ( Amaranthus retroflexus ), Cyperus serotinus , Echinochloa crus galli , Matricaria inodora , Setaria viridis , Stellaria media , Veronica persica and Viola tricolor ) the activity.
將單子葉或雙子葉雜草或作物植物之種子置於木纖維盆之砂質壤土中，以土壤覆蓋，良好生長條件下，使其於溫室中生長。播種2至3週後，於一葉期內處理測試植物。然後將調配成可濕性粉劑(WP)或乳化濃縮物(EC)形式之根據本發明之化合物，呈水性懸浮液或乳液形式，以600至800公升/公頃(轉換)之水(添加0.2%潤濕劑)施加率，噴灑於植物之綠色部位。於最適生長條件下，將測試植物放置於溫室中約3週後，與未經處理之對照組比較，進行製劑活性之視覺評分[除草活性百分比(%)：100%活性=植物已死，0%活性=類似對照組植物]。於此，舉例而言，於80公克/公頃之施加率下，化合物編號1-028、1-138及1-270顯示各具至少80%強度之對抗苘麻、稗草、母菊、狗尾草、繁縷與婆婆納之活性。 Seeds of monocotyledonous or dicotyledonous weeds or crop plants are placed in sandy loam of wood fiber pots, covered with soil, and grown in a greenhouse under good growing conditions. After 2 to 3 weeks of sowing, the test plants were treated during the one leaf period. The compound according to the invention in the form of a wettable powder (WP) or an emulsified concentrate (EC) is then formulated as an aqueous suspension or emulsion in an amount of from 600 to 800 liters per hectare (converted) of water (0.2% added) Wetting agent) application rate, sprayed on the green part of the plant. Under optimal growth conditions, the test plants were placed in the greenhouse for about 3 weeks, and the visual score of the preparation activity was compared with the untreated control group [% herbicidal activity (%): 100% activity = plant dead, 0 % activity = similar to control plants]. Here, for example, at an application rate of 80 g/ha, compound numbers 1-028, 1-138, and 1-270 show at least 80% strength against ramie, valerian, mother chrysanthemum, foxtail, The enthusiasm and the activity of the mother-in-law.
Claims (13)
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