TW201127285A - Substituted cyanobutyrates having herbicidal action - Google Patents

Substituted cyanobutyrates having herbicidal action Download PDF

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TW201127285A
TW201127285A TW99134510A TW99134510A TW201127285A TW 201127285 A TW201127285 A TW 201127285A TW 99134510 A TW99134510 A TW 99134510A TW 99134510 A TW99134510 A TW 99134510A TW 201127285 A TW201127285 A TW 201127285A
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alkyl
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TW99134510A
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Andrea Vescovi
Robert Reinhard
Bernd Sievernich
Cyrill Zagar
Elmar Kibler
Ricarda Niggeweg
Toralf Kuehn
Matthias Witschel
William Karl Moberg
Rapado Liliana Parra
Tao Qu
Frank Stelzer
Andree Van Der Kloet
Thomas Seitz
Thomas Ehrhardt
Klaus Kreuz
Klaus Grobmann
Anna Aleksandra Michrowska-Pianowski
Anja Simon
Richard Roger Evans
Eike Hupe
Klaus Reinhard
Matthias Bergtold
Susanne Noreen Evelyn Kolle
Stefan Tresch
Dschun Song
Julia Major
Johannes Hutzler
Trevor William Newton
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/20—Oxygen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Substituted cyanobutyrates of the formula I in which the variables are defined according to the description, processes and intermediates for preparing the compounds of the formula I and the N-oxides thereof, the agriculturally usable salts thereof, compositions comprising them and their use as herbicides, and also methods for controlling unwanted vegetation.

Description

201127285 六、發明說明： 【發明所屬之技術領域】 本發明係關於經取代之式I氰基丁酸化物：201127285 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to substituted cyanobutyrate of formula I:

其中代號具有以下含義： R 為鹵素；氰基；硝基；Ci-c4烷基；d-Q鹵烷基； i C2-C6稀基；C2.C6快基；Z-三（Cl_C4烧基）石夕烷基， R 為氫，Z-CN ; Cl-C8烧基；Z.C3-C6環炫基；CVCd 院基；c3-c8稀基；z_c3_c6m埽基；c3_c8炔基；z_ (二-C丨-c4院基）石夕烷基；z_c(=0)_Ra; z p(=〇)(Ra)2; Z苯基，含有1、2、3或4個選自由Ο、N及S組成之 群之雜原子的3至7員單環或9或1〇員雙環飽和、不 飽和b或方族雜環，該雜環可部分或完全經基團1^及/ 或妒取代且經由碳或氮連接， 為氯’ OH ; C〗-C8^基；鹵院基；Z-C3-C6 长燒基’（：2-(：8稀基；Z-C5-C6-環稀基；C2-CW 基’ Z-Ci-C：6院氧基；Z-CVC4鹵烧氧基；z-c3-c8 稀氧基，z-c3-c8炔氧基；NRiRii ; Ci_c6烷基磺 酿其 · 7 , 一 ' 土 ’ -(二-Ci-C4烷基）矽烷基；z_苯基；z-笨 氧基，Z-苯基胺基；或含有2 ' 2、3或4個選自 151170.doc 由〇、N及S組成之群之雜原子的⑽員單環或9 或10員雙環雜環’其中該等環狀基團未經取代 或經1、2、3或4個基團Rb取代；Wherein the code has the following meanings: R is halogen; cyano; nitro; Ci-c4 alkyl; dQ haloalkyl; i C2-C6 dilute; C2.C6 fast radical; Z-tri (Cl_C4 alkyl) Alkyl, R is hydrogen, Z-CN; Cl-C8 alkyl; Z.C3-C6 cyclos; CVCd; c3-c8 dilute; z_c3_c6m fluorenyl; c3_c8 alkynyl; z_ (di-C丨-c4 院基), 石 烷基 alkyl; z_c(=0)_Ra; zp(=〇)(Ra)2; Z phenyl, containing 1, 2, 3 or 4 groups selected from Ο, N and S a 3 to 7 membered monocyclic or 9 or 1 membered bicyclic saturated, unsaturated b or aristocratic heterocyclic ring of a hetero atom which may be partially or completely substituted by a group 1 and/or a hydrazine and via carbon or nitrogen Linked, is chloro ' OH ; C 〗 〖C8 ^ base; halogen courtyard; Z-C3-C6 long alkyl ' (: 2- (: 8 thin base; Z-C5-C6- ring thin base; C2-CW Base 'Z-Ci-C: 6-oxooxy; Z-CVC4 halo-oxyl; z-c3-c8 diloxy, z-c3-c8 alkynyl; NNiRii; Ci_c6 alkyl sulfonate · 7 a 'soil'-(di-Ci-C4 alkyl)decylalkyl; z-phenyl; z-phenyloxy, Z-phenylamino; or 2' 2, 3 or 4 selected from 151170.doc (10) member single ring or 9 of heteroatoms consisting of 〇, N and S Or a 10-membered bicyclic heterocyclic ring wherein the cyclic groups are unsubstituted or substituted with 1, 2, 3 or 4 groups Rb;

Ri、R,i彼此獨立為氫；Μ烷基；Cl_C4鹵烷 基；C3-C8烯基；c3_c8炔基；Z_C3_C4 烷基；z_Cl_C8院氧基；Z-Cl-C8函烷氧 基；Z-C(=〇)_ra，其中r、〇h^Ci C4 烷氧基； R及R與其所連接之氮原子一起亦可形成含有 或4個選自由0、N&S組成之群之雜原 子的5或6員單環或9或10員雙環雜環； 彼此獨立為 Z-CN;Z-OH;z_n〇2;ZHCi C8 烷基；CVC4函院基；c2_c8烯基；C2_c8炔基； z-c丨-c8烷氧基；z_Ci_C8函烷氧基；z_c3_Ci〇環 垸基，〇-Z-C3-C1()環烧基；Z-C(=〇)-Ra ; NRiRii ; Z-(二·Cl_C4烷基）矽烷基；z_笨基及s(〇)mRbb; 其中Rbb為C1-CS烷基或(VC6鹵烷基； ni 為 〇、1 或 2 ;Ri, R, i are each independently hydrogen; decylalkyl; Cl_C4 haloalkyl; C3-C8 alkenyl; c3_c8 alkynyl; Z_C3_C4 alkyl; z_Cl_C8 alkoxy; Z-Cl-C8 alkoxy; ZC =〇)_ra, wherein r, 〇h^Ci C4 alkoxy; R and R together with the nitrogen atom to which they are attached may also form 5 or 4 heteroatoms selected from the group consisting of 0, N&S or 6 membered monocyclic or 9 or 10 membered bicyclic heterocyclic ring; independently of each other as Z-CN; Z-OH; z_n〇2; ZHCi C8 alkyl; CVC4 functional base; c2_c8 alkenyl; C2_c8 alkynyl; zc丨-c8 Alkoxy; z_Ci_C8 alkoxy; z_c3_Ci〇cyclodecyl, 〇-Z-C3-C1()cycloalkyl; ZC(=〇)-Ra ; NRiRii ; Z-(di·Cl_C4 alkyl)decyl ; z_stupyl and s(〇)mRbb; wherein Rbb is C1-CS alkyl or (VC6 haloalkyl; ni is 〇, 1 or 2;

Rb與連接至相鄰碳原子之基團Rb—起亦可形成5 或6員飽和或部分或完全不飽和環，除碳原子以 外，該環亦可含有i、2或3個選自由〇、N&s組 成之群之雜原子； 為共價鍵或Ci-Cs伸烷基； 為0、1、2、3、4或 5 ; 201127285 R2、R3彼此獨立為鹵素；氰基；硝基；Cl-c4院基；（：丨-(：4 烧氧基；S(0)mRb、NRiR" ; Cl_C4 函烷基；Ci_C4 齒 烷氧基； 其中在基團R及R1及其亞取代基中’碳鏈及/或環狀基團可 部分或完全經基團Ra及/或Rb取代， 其限制條件為 a) 若n=〇且R1為乙基，則R2及R3不同時為氯；及 b) 若n=Ul2, Ri為曱基，R2為氟且r3為氟、氣或溴，則尺 不為氟； 或其N-氧化物或農業上適合之鹽。 此外’本發明係關於製備式Z化合物及其N_氧化物、其 農業上可用之鹽的方法及中間物，係關於包含其之組合 物，且係關於其用作除草劑，亦即用於控制有害植物之用 途，且亦係關於控制不要之植被的方法，其包含使除草有 效量之至少一種式丨化合物或其農業上適合鹽作用於植 物、其種子及/或其棲息地。 本發明之其他實施例可見於申請專利範圍、說明書及實 例中。應瞭解，本發明標的之上述特徵及待於下文中繼續 說明之特徵在不背離本發明範疇的情況下不僅可以各別既 定組合應用，且亦可以其他組合應用。 【先前技術】 EP-A 5 341、EP-A 266 725、ΕΡ·Α 270 830、jp 04/297 JP 04/297 455及jp 05/058 979中已知除草氰基丁酸化 物…、:而，其除草作用，尤其在低施用率下之除草作用， 151170.doc 201127285 及/或其與作物植物之相容性仍需改良。 【發明内容】 本發明之一目的為提供具除草作用之化合物。詳言之提 供具強除草作用之活性化合物，尤其即使在低施用率下， 該等活性化合物與作物植物之相容性亦足以滿足商業應 此等目的及其他目的由最初定義之式〖化合物及其Ν•氧 化物以及其農業上適合之鹽達成。 本發明化合物可類似於所引用之文獻中所述之合成途 徑，根據有機化學之標準方法，例如根據以下合成途徑製 可根據邁克加成（Michael addition)使式Π之苯基乙腈衍 生物與式III之肉桂酸酯衍生物反應，得到式〗化合物。在 式II及式III中，代號具有針對式〗所給之含義。Rb may also form a 5 or 6 membered saturated or partially or fully unsaturated ring together with a group Rb attached to an adjacent carbon atom. The ring may contain, in addition to a carbon atom, i, 2 or 3 selected from the group consisting of a hetero atom of a group consisting of N&s; a covalent bond or an alkyl group of Ci-Cs; 0, 1, 2, 3, 4 or 5; 201127285 R2, R3 are each independently halogen; cyano; nitro; Cl-c4 hospital base; (: 丨-(:4 alkoxy; S(0)mRb, NNiR"; Cl_C4 functional alkyl; Ci_C4 dentateoxy; wherein in the groups R and R1 and their sub-substituents 'The carbon chain and/or the cyclic group may be partially or completely substituted by the groups Ra and/or Rb, the limiting condition being a) if n=〇 and R1 is ethyl, then R2 and R3 are not simultaneously chlorine; b) If n = Ul2, Ri is a fluorenyl group, R2 is fluorine and r3 is fluorine, gas or bromine, then the ruler is not fluorine; or its N-oxide or agriculturally suitable salt. Further, the present invention relates to a process and an intermediate for the preparation of a compound of the formula Z and an N-oxide thereof, an agriculturally usable salt thereof, relating to a composition comprising the same, and for use as a herbicide, that is, Controlling the use of harmful plants, and also as a method of controlling unwanted vegetation, comprising causing a herbicidally effective amount of at least one compound of the formula or an agriculturally suitable salt thereof to act on the plant, its seeds and/or its habitat. Other embodiments of the invention can be found in the scope of the patent application, the description and the examples. It is to be understood that the above-described features of the subject matter of the present invention and the features to be further described hereinafter may be applied not only in the respective combinations but also in other combinations without departing from the scope of the invention. [Prior Art] It is known that herbicidal cyanobutyrate is used in EP-A 5 341, EP-A 266 725, ΕΡ Α 270 830, jp 04/297 JP 04/297 455 and JP 05/058 979. Its herbicidal action, especially at low application rates, 151170.doc 201127285 and / or its compatibility with crop plants still needs improvement. SUMMARY OF THE INVENTION One object of the present invention is to provide a herbicidal compound. In particular, the active compounds having a strong herbicidal action are provided, especially at low application rates, the compatibility of the active compounds with crop plants is sufficient for commercial purposes and other purposes. Its bismuth oxides and its agriculturally suitable salts are achieved. The compound of the present invention can be similar to the synthetic route described in the cited literature, according to the standard method of organic chemistry, for example, according to the following synthetic route, according to Michael addition, the phenylacetonitrile derivative and formula of the formula can be made according to Michael addition. The cinnamate derivative of III is reacted to give a compound of the formula. In Formula II and Formula III, the code has the meaning given to the formula.

此反應通常在，較佳之溫度 下，在惰性有機溶劑中，在鹼及/或催化劑[參看乂 心c· (1945)，第438頁]存在下進行。 適合溶劑為脂族烴、芳族烴、鹵化烴、醚（諸如***、 二異丙醚、第三丁基f基醚、 噁烷、苯甲醚及四氫呋喃 151170.doc 201127285 (THF))、腈、酮、醇（諸如甲醇、乙醇、正丙醇異丙 醇、正丁醇及第三丁醇）以及二甲亞颯、二曱基曱醯胺 (DMF)及二甲基乙醯胺（DMA)及水，尤佳為thf及甲醇。 亦可此使用所提及溶劑之混合物。 適合鹼通常為無機化合物，諸如鹼金屬及鹼土金屬氫氧 化物、驗金屬及驗土金屬氧化物、驗金屬及驗土金屬氫化 物、鹼金屬胺化物（諸如胺化鋰、胺化鈉及胺化鉀）、鹼金 屬及鹼土金屬碳酸鹽，以及鹼金屬碳酸氫鹽、有機金屬化 合物（尤其鹼金屬烷基）、齒化烷基鎂以及鹼金屬及驗土金 屬醇鹽（諸如甲醇鈉、乙醇鈉、乙醇鉀、第三丁醇钟及甲 醇鎖（dimethoxymagnesium));此外有機鹼，例如三級胺、 吡啶、經取代吡啶以及雙環胺。尤佳為第三丁醇鉀、雙 (二甲基石夕烧基）胺基鐘及7-甲基-1，5，7-三氮雜雙環[4.4.0] 癸-5-稀。 該等鹼通常以催化量使用；然而其亦可以等莫耳量、過 量或（若適當）以溶劑形式使用。 適用作酸性催化劑者為無機酸，諸如氫氟酸、鹽酸、氫 漠酸、硫酸及過風酸；路易斯酸（Lewis acid)，諸如三氣化 硼、三氣化鋁、氣化鐵（III)、氣化錫（IV)、氯化鈦（IV)、 二氟曱續酸銳（HI)及氣化辞（II);以及有機酸，諸如甲 酸、乙酸、丙酸、草酸、曱苯磺酸、笨磺酸、樟腦磺酸、 檸檬酸及三氟乙酸。 該等酸通常以催化量使用；然而其亦可以等莫耳量、過 量或（若適當）以溶劑形式使用。 151170.doc -8 - 201127285 或者，式i化合物亦可藉由其他氰基丁酸化物之酯基轉 移獲得此可藉由各種方法進行，例如藉由下述方法： 酗基轉移可在分子篩存在下，於醇Rl_〇H中，（若適當） 在非質子性溶劑中進行。此反應通常在代至1贼、較佳 2〇c至8〇t之溫度下，在路易斯酸或布忍斯特酸（Br0nsted aCid)或酶存在下進行[參看 J. Org. Chem. 2002, 67, 431]。 適合溶劑為脂族烴、芳族烴、齒化烴、醚、腈以及二甲 亞石風（DMSO)、DMF及DMA，尤佳為醇rLoh。亦可能使 用所提及溶劑之混合物。 或者，酯基轉移可藉由使其他氰基丁酸化物酸性或鹼性 水解（a) ’繼而與醇ri_〇h&應進行。此等反應通常在 至120 C、較佳20 C至50。(：之溫度下，在驗或酸及/或催化 劑存在下進行[參看 J. Am_ Chem. Soc. 2007，129 (43)， 13321 , J. 〇rg- chem. 1984, 49 (22), 4287.] » 適合溶劑為脂族烴、芳族烴、函化烴、醚（諸如***、 二異丙峻、第三丁基曱基醚、二噁烷、苯甲醚及THF)、 腈、酮、醇（諸如曱醇、乙醇、正丙醇、異丙醇、正丁醇 及第二丁醇）以及DMSO、DMF及DMA及水，尤佳為（a) 水、THF ; (bOR^OH。亦可能使用所提及溶劑之混合物。 適合鹼通常為無機化合物，諸如鹼金屬及鹼土金屬氫氧 化物（諸如氫氧化鋰、氫氧化鈉、氫氧化鉀及氫氧化鈣）、 鹼金屬及鹼土金屬氧化物、鹼金屬及鹼土金屬氫化物、鹼 金屬胺化物、鹼金屬及鹼土金屬碳酸鹽以及鹼金屬碳酸氫 鹽、有機金屬化合物（尤其鹼金屬烷基）、鹵化烷基鎂以及 151170.doc 201127285 鹼金屬及鹼土金屬醇鹽及甲醇鎂；此外有機鹼，例如三級 胺及N-甲基哌啶、吡啶、經取代吡啶以及雙環胺。尤佳為 氫氧化鋰。 該等驗通常使用催化量；然而其亦可使用等莫耳量、過 量，或（若適當）作為溶劑使用。 適用作酸及酸性催化劑者為無機酸，諸如氫氟酸、鹽 酸、氫溴酸、硫酸及過氯酸；路易斯酸，諸如三氣化棚、 二氯化铭、氯化鐵（III)、氯化錫（IV)、氣化鈦（IV)及氯化 鋅（II);以及有機酸’諸如甲酸 '乙酸、丙酸、草酸、甲 本％酸、本靖酸、掉腦續酸、棒樣酸及三氟乙酸。 該等酸通常使用催化量；然而其亦可使用等莫耳量、過 量或（若適當）作為溶劑使用。 製備化合物I所需之起始物質可自文獻已知或可根據所 引用之文獻製備。 反應混合物係依慣用方式操作，例如與水混合、分離各 相，且（若適當）層析純化粗產物。有些中間物及終產物係 呈無色或淺棕色黏性油狀物形式獲得，將其在減壓下及適 度加溫下純化或去除揮發性組份。若獲得呈固體之中間物 及終產物，則亦可藉由再結晶或消解法進行純化。 若個別化合物I不能藉由上述途徑獲得’則其可藉由其 他化合物I衍生製備。 若該合成法產生異構體之混合物，則通常需要分離但 並非必需，因為有些情況下，個別異構體可在使用處理期 間或施用期間（例如在光、酸或鹼之作用下）相互轉化。該 151170.doc • 10· 201127285 專轉化作用亦可能在施用之後發生，例如在處理植物的情 況下’在接受處理之植物中或在需要控制之有害植物中發 生。 針對本發明化合物之取代基所提及之有機部分為個別列 舉的個別基團成員之統稱術語。所有烴鏈，諸如烷基、鹵 烧基、烯基、炔基’及在烷氧基、自烷氧基、烷基胺基、 二烧基胺基' N-烷基磺醯基胺基、烯氧基、炔氧基、烷氧 基胺基、烷基胺基磺醯基胺基、二烷基胺基磺醯基胺基、 烯基胺基、炔基胺基、N-(烯基）-N-(烧基）胺基、N-(炔基）-N-(炫•基）胺基、N-(烷氧基）-N-(烷基）胺基、N-(烯基）-N-(烷 氧基）胺基或N-(炔基）-N-(烷氧基）胺基中之烷基部分及烯 基部分可為直鏈或分支鏈。 字首Cn-Cm指示烴單元中碳之各別數目。除非另外指 明’否則鹵化取代基較佳帶有1至5個相同或不同鹵素原 子’尤其氟原子或氣原子。 在各情況下，鹵素含義表示氟、氣、溴或峨。 其他含義之實例為： 烷基及例如烷氧基、烷基胺基、二烷基胺基、N-烷基磺 酿基胺基、烷基胺基磺醯基胺基、二烷基胺基磺醯基胺 基、N-(烯基）-N-(烷基）胺基、N-(炔基）-N-(烷基）胺基、N-(烷氧基）-N-(烷基）胺基中之烷基部分：具有一或多個碳原 子，例如1或2個、1至4個或1至6個碳原子的飽和直鏈或分 支鏈烴基，例如烷基，諸如曱基、乙基、丙基、1-甲 基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙 151170.doc • 11 - 201127285 基、戊基、1-甲基丁基、2-甲基丁基、3 -甲基丁基、2，2-二甲基丙基、1-乙基丙基、己基、1，1-二甲基丙基、l，2-二 甲基丙基、1-曱基戊基、2-甲基戊基、3-甲基戊基、4_ψ 基戊基、Μ-二曱基丁基、1，2·二曱基丁基、ι，3-二甲基丁 基、2,2-二甲基丁基、2,3-二曱基丁基、3,3-二曱基丁基、 1- 乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1，2,2-三曱 基丙基、1-乙基-1-曱基丙基、1-乙基-2-曱基丙基。在本發 明之一實施例中，烧基表示小烧基，諸如烧基。在 本發明之另一實施例中，烷基表示相對較大烷基，諸如 〇5-(：6烷基。 鹵烷基：如上所述之烷基’其一些或全部氫原子經鹵素 原子（諸如氟、氯、溴及/或碘）取代，例如氯曱基、二氣曱 基、三氣曱基、氟曱基、二氟曱基、三氟曱基、氯氟甲 基、二氯氟曱基、氣二氟曱基、2-氟乙基、2-氯乙基、2_ 溴乙基、2-碘乙基、2,2-二氟乙基、2,2,2-三氟乙基、2_氯_ 2- 氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基、五氟乙基、2_氟丙基、3_氟丙基、2,2_二氟丙 基' 2’3-二氟丙基、2_氣丙基、3-氯丙基、2，3-二氯丙基、 2-溴丙基、3-溴丙基、3,3,3-三氟丙基、3,3,3-三氯丙基、 2,2’3,3,3·五氟丙基、七氟丙基、1-(氟甲基）2氟乙基、！· (氣曱基）-2-氯乙基、！_(溴曱基）·2_溴乙基、4氟丁基、4_ 氯丁基、4-溴丁基及九氟丁基。 環烷基及例如環烷氧基或環烷基羰基中之環烷基部分： 具有一個或二個以上碳原子，例如3至6個碳環成員的單環 151170.doc -12· 201127285 飽和烴基’諸如環丙基、環丁基、環戊基及環己基。 烯基及例如烯基胺基、烯氧基、N-(烯基）·ν·(烷基）胺 基、Ν-(婦基）_Ν•(烷氧基）胺基中之烯基部分：具有兩個或 兩個以上碳原子，例如2至4個、2至6個或3至6個碳原子， 且任何位置具有雙鍵的單不飽和直鏈或分支鏈烴基，例如 CyC6烯基，諸如乙烯基、卜丙烯基、2_丙烯基、^甲基乙 烯基、1-丁烯基、2-丁烯基、3_ 丁烯基、丨_曱基丙烯 基、2-甲基-1·丙烯基、丨_甲基_2_丙烯基、2甲基·孓丙烯 基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1_曱基 1- 丁烯基、2-曱基-1-丁烯基、3_甲基丁烯基、i•甲基1 丁烯基、2-甲基-2-丁烯基、3_曱基_2_丁烯基、丨·甲基 丁烯基' 2-曱基-3-丁烯基、3_曱基_3_丁烯基、la•二甲基 2- 丙烯基、ι，2-二甲基丙烯基、j，2二甲基_2_丙烯基、 1- 乙基-1-丙烯基、1-乙基_2_丙烯基、卜己烯基、2己烯 基、3-己烯基、4_己烯基、5_己烯基、丨曱基_丨·戊烯基、 2- 甲基-1-戊烯基、3-甲基-丨·戊烯基、4_甲基_丨_戊烯基、！ 甲基-2-戊烯基、2-甲基-2-戊烯基、3_甲基_2_戊烯基、馭 甲基-2-戊烯基、！_甲基_3_戊烯基、2_甲基_3_戊烯基 '夂 • 曱基·3-戊烯基、4_甲基-3-戊烯基、1_甲基_4·戊烯基、夂 • 曱基-4-戊烯基、3-曱基-4-戊烯基、4_甲基_4_戊烯基、 二曱基-2-丁烯基、U_二甲基_3_ 丁烯基、12_二甲基j 丁 烯基、1，2-二甲基-2-丁烯基、L2-二曱基_3_丁烯基、 二曱基-1-丁烯基、1，3-二甲基·2_ 丁烯基、^―二甲基」、丁 烯基、2,2-二曱基-3-丁烯基、2,3_二甲基“·丁烯基、2,夂 151170.doc -13- 201127285 二甲基·2-丁烯基、2,3·二甲基-3_丁烯基、3,3·二甲基―卜丁 烯基、3,3-二甲基-2-丁烯基、卜乙基-丨-丁烯基、丨·乙基·2_ 丁烯基、1-乙基-3-丁烯基、2_乙基_i_丁烯基、2乙基_2· 丁烯基、2-乙基-3-丁烯基、丨，丨，2_三甲基-2-丙烯基、^乙 基-1-甲基_2·丙烯基、1·乙基_2·曱基丙烯基、丨乙基_2· 甲基-2-丙烯基。 環烯基：具有3至6個，較佳5或ό個碳環成員的單環單不 飽和烴基，諸如環戊烯_丨_基、環戊烯_3_基、環己烯 基、1哀己稀-3-基、環己稀-4·基。 炔基及例如炔氧基、炔基胺基、Ν-(炔基）-Ν-(烷基）胺基 或Ν-(炔基）-Ν-(烧氧基）胺基中之炔基部分：具有兩個或兩 個以上碳原子’例如2至4個、2至6個或3至6個碳原子，且 任何位置具有參鍵的直鍵或分支鍵煙基，例如匚2_(36快 基，諸如乙炔基、1-丙炔基、2_丙炔基、1-丁炔基、2-丁 炔基、3-丁炔基、1·曱基-2-丙炔基、1-戊炔基、2-戊炔 基、3-戊炔基、4-戊炔基 '卜甲基-2-丁炔基、1-甲基-3-丁 炔基、2-甲基-3-丁炔基、3-甲基-1-丁炔基、1,1-二甲基-2-丙炔基、1-乙基-2-丙炔基、1-己炔基、2_己炔基、3-己炔 基、4·己炔基、5-己炔基、1-甲基-2-戊炔基、1-曱基-3-戊 炔基、1-甲基-4-戊炔基、2-曱基-3·戊炔基、2-甲基-4-戊 快基、3 -甲基-1-戊快基、3 -甲基-4 -戊块基、4-甲基-1-戍 炔基、4-曱基-2-戊炔基、1，1-二甲基-2-丁炔基、1，1-二甲 基-3-丁炔基、1，2-二甲基-3-丁炔基、2,2-二甲基-3-丁炔 基、3,3-二曱基-1-丁炔基、1-乙基-2· 丁炔基、1·乙基-3-丁 151170.doc -14· 201127285 炔基、2-乙基-3-丁炔基、1-乙基-!-▼基-2-丙炔基。 炫氧基··如上所定義之烷基，其經由氧原子連接，例如 f氧基、乙氧基、正丙氧基、i-甲基乙氧基、丁氧基、^ f基丙氧基、2-甲基丙氧基或ι，ΐ-二甲基乙氧基、戊氧 基、1-甲基丁氧基、2-甲基丁氧基、3 -甲基丁氧基、ι，ι· 二甲基丙氧基、i，2_二甲基丙氧基、2,2_二甲基丙氧基、^ 乙基丙氧基、己氧基、卜甲基戊氧基、2_甲基戊氧基、3_ 甲基戍氧基、4_甲基戊氧基、1，1_二甲基丁氧基、1，2-二曱 基丁氧基、1，3-二甲基丁氧基、2,2_二甲基丁氧基、2,3_二 甲基丁氧基、3,3-二甲基丁氧基、i•乙基丁氧基、2·乙基 丁氧基、1，1，2-三甲基丙氧基、12 2_三甲基丙氧基、丨·乙 基-1-曱基丙氧基或丨_乙基_2_甲基丙氧基。 5或6員雜環：具有5或6個環原子，丨、2、3或4個環原子 為選自由Ο、S及N組成之群之雜原子的環狀基團，其中該 %狀基團為飽和、部分不飽和或芳族。 式I化合物含有兩個對掌性中心，且視取代模式而定可 含有-或多個其他對掌性中心。因此，本發明化合物可以 ’屯對映異構體或非對映異構體形式或對映異構體或非對映 異構H物之形式存在。本發明提供純對映異構體或非 對映異構體及其混合物。This reaction is usually carried out at a preferred temperature in an inert organic solvent in the presence of a base and/or a catalyst [see c心c· (1945), p. 438]. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers (such as diethyl ether, diisopropyl ether, tert-butyl f-ether ether, oxane, anisole and tetrahydrofuran 151170.doc 201127285 (THF)), nitrile , ketones, alcohols (such as methanol, ethanol, n-propanol isopropanol, n-butanol and tert-butanol) and dimethyl hydrazine, dimethyl decyl amide (DMF) and dimethyl acetamide (DMA) And water, especially for thf and methanol. Mixtures of the solvents mentioned may also be used herein. Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides, metal and soil metal oxides, metal and soil metal hydrides, alkali metal amines (such as lithium amination, sodium amination and amines) Potassium), alkali metal and alkaline earth metal carbonates, and alkali metal hydrogencarbonates, organometallic compounds (especially alkali metal alkyls), alkylated magnesium alkyls, and alkali metals and soil metal alkoxides (such as sodium methoxide, ethanol) Sodium, potassium ethoxide, third butanol, and dimethoxymagnesium; further organic bases such as tertiary amines, pyridines, substituted pyridines, and bicyclic amines. It is especially preferred to be potassium tert-butoxide, bis(dimethyl oxalate)amine, and 7-methyl-1,5,7-triazabicyclo[4.4.0] 癸-5-dilute. These bases are usually used in catalytic amounts; however, they may also be used in molar form, in excess or, if appropriate, in the form of a solvent. Suitable as acidic catalysts are inorganic acids, such as hydrofluoric acid, hydrochloric acid, hydrogen desert acid, sulfuric acid and perylene acid; Lewis acid, such as tri-carbide, tri-aluminum, and iron (III) , vaporized tin (IV), titanium (IV) chloride, difluoroanthracene (HI) and gasification (II); and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, terephthalic acid , stupid sulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid. These acids are usually used in catalytic amounts; however, they may also be used in molar form, in excess or, if appropriate, in the form of a solvent. Alternatively, the compound of formula i can also be obtained by transesterification of other cyanobutyrate by various methods, for example by the following method: thiol transfer can be in the presence of molecular sieves In the alcohol Rl_〇H, if appropriate, in an aprotic solvent. This reaction is usually carried out in the presence of a Lewis acid or Bronsted aCid or an enzyme at a temperature of 1 贼c to 8 〇t [see J. Org. Chem. 2002, 67 , 431]. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, dentate hydrocarbons, ethers, nitriles and dimethyl sulphur (DMSO), DMF and DMA, and more preferably alcohols rLoh. Mixtures of the solvents mentioned can also be used. Alternatively, transesterification can be carried out by acidic or alkaline hydrolysis of other cyanobutyrate (a)' followed by alcohol ri_〇h& These reactions are usually at 120 C, preferably 20 C to 50. (At the temperature, in the presence of an acid or / or catalyst [see J. Am_ Chem. Soc. 2007, 129 (43), 13321, J. 〇rg- chem. 1984, 49 (22), 4287 .] » Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, functional hydrocarbons, ethers (such as diethyl ether, diisopropyl, tert-butyl decyl ether, dioxane, anisole and THF), nitriles, ketones , alcohol (such as decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol and second butanol) and DMSO, DMF and DMA and water, especially preferably (a) water, THF; (bOR^OH. It is also possible to use mixtures of the solvents mentioned. Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides (such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide), alkali metals and alkaline earth metals. Oxides, alkali metal and alkaline earth metal hydrides, alkali metal aminations, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds (especially alkali metal alkyl), alkyl magnesium halides and 151170.doc 201127285 Alkali metal and alkaline earth metal alkoxides and magnesium methoxide; further organic bases such as tertiary amines and N-A Piperidine, pyridine, substituted pyridine and bicyclic amine. Particularly preferred is lithium hydroxide. The test is usually carried out using a catalytic amount; however, it can also be used in an equivalent molar amount, in excess, or (if appropriate) as a solvent. Acid and acid catalysts are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid; Lewis acids such as three gasification sheds, dichlorinated iron, iron (III) chloride, chlorination Tin (IV), vaporized titanium (IV) and zinc (II) chloride; and organic acids such as formic acid 'acetic acid, propionic acid, oxalic acid, methylated acid, Benzoic acid, cerebral acid, bar acid And trifluoroacetic acid. The acids are usually used in catalytic amounts; however, they may also be used in molar excess, in excess or, if appropriate, as a solvent. The starting materials required for the preparation of the compound I may be known from the literature or may be Preparation of the cited literature. The reaction mixture is operated in a conventional manner, for example by mixing with water, separating the phases, and (if appropriate) purifying the crude product. Some intermediates and final products are colorless or light brown viscous oils. Obtained in form, under reduced pressure and Purification or removal of volatile components by heating. If intermediates and final products are obtained as solids, they can also be purified by recrystallization or digestion. If individual compounds I cannot be obtained by the above route, then they can be Derivatization by other compound I. If the synthesis produces a mixture of isomers, separation is usually required but not necessary, as in some cases individual isomers may be used during processing or during application (eg in light, acid) 151170.doc • 10· 201127285 The specific transformation may also occur after application, for example in the case of treatment of plants in the treated plants or in the harmful plants that need to be controlled . The organic moiety referred to for the substituent of the compound of the present invention is a collective term for the individual group members listed individually. All hydrocarbon chains, such as alkyl, haloalkyl, alkenyl, alkynyl' and in alkoxy, alkoxy, alkylamino, dialkylamino 'N-alkylsulfonylamino, Alkenyloxy, alkynyloxy, alkoxyamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, alkenylamino, alkynylamino, N-(alkenyl) -N-(alkyl)amino, N-(alkynyl)-N-(hexyl)amino, N-(alkoxy)-N-(alkyl)amino, N-(alkenyl) The alkyl moiety and the alkenyl moiety in the -N-(alkoxy)amino group or the N-(alkynyl)-N-(alkoxy)amino group may be a straight or branched chain. The prefix Cn-Cm indicates the respective number of carbons in the hydrocarbon unit. Unless otherwise indicated, 'halogenated substituents preferably have from 1 to 5 identical or different halogen atoms', especially fluorine or gas atoms. In each case, halogen means fluorine, gas, bromine or hydrazine. Examples of other meanings are: alkyl groups and, for example, alkoxy groups, alkylamino groups, dialkylamino groups, N-alkylsulfonic acid amine groups, alkylaminosulfonylamino groups, dialkylamino groups Sulfhydrylamino, N-(alkenyl)-N-(alkyl)amino, N-(alkynyl)-N-(alkyl)amine, N-(alkoxy)-N-(alkane Alkyl moiety in the amino group: a saturated straight or branched chain hydrocarbon group having one or more carbon atoms, for example 1 or 2, 1 to 4 or 1 to 6 carbon atoms, such as an alkyl group such as hydrazine Base, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl 151170.doc • 11 - 201127285 ke, ke Base, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropane Base, l,2-dimethylpropyl, 1-decylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentylpentyl, fluorenyl-dimercaptobutyl, 1,2· Dimercaptobutyl, iota, dimethylbutyl, 2,2-dimethylbutyl, 2,3-didecylbutyl, 3,3-didecylbutyl, 1-ethyl Butyl, 2-ethylbutyl, 1,1,2-trimethylpropane , 1,2,2-Yue propyl, 1-ethyl-propyl Yue, Yue-yl 1-ethyl-propyl. In one embodiment of the invention, the alkyl group represents a small alkyl group, such as a burn group. In another embodiment of the invention, alkyl denotes a relatively large alkyl group, such as 〇5-(:6 alkyl. Haloalkyl: alkyl as described above, some or all of its hydrogen atoms are passed through a halogen atom ( Substituting such as fluorine, chlorine, bromine and/or iodine, for example, chlorohydrazine, dihalofluorenyl, trishydrazinyl, fluoroindolyl, difluoroindolyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoro Sulfhydryl, gas difluorodecyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl Base, 2_chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, five Fluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl '2'3-difluoropropyl, 2-propylpropyl, 3-chloropropyl, 2,3- Dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2'3,3,3·5 Fluoropropyl, heptafluoropropyl, 1-(fluoromethyl) 2 fluoroethyl, !·(gas sulfhydryl)-2-chloroethyl, !_(bromoindolyl)·2_bromoethyl, 4 Fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl. Cycloalkyl and, for example, cycloalkoxy or cycloalkylcarbonyl a cycloalkyl moiety in the group: a single ring having one or two or more carbon atoms, for example, 3 to 6 carbon ring members 151170.doc -12· 201127285 saturated hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl And a cyclohexyl group, an alkenyl group and, for example, an alkenylamino group, an alkenyloxy group, an N-(alkenyl).v.(alkyl)amino group, a fluorene-(inviyl)-indolyl group Alkenyl moiety: a monounsaturated straight or branched chain hydrocarbon radical having two or more carbon atoms, for example 2 to 4, 2 to 6 or 3 to 6 carbon atoms, and having a double bond at any position, for example CyC6 alkenyl group, such as vinyl, propylene, 2-propenyl, methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, fluorenyl fluorenyl, 2-methyl Base-1·propenyl, 丨-methyl-2-propenyl, 2-methyl·decenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 _ mercapto 1-butenyl, 2-mercapto-1-butenyl, 3-methylbutenyl, i•methyl 1 butenyl, 2-methyl-2-butenyl, 3_ Indenyl-2-butenyl, 丨·methylbutenyl '2-mercapto-3-butenyl, 3-hydrazino-3-butenyl, la•dimethyl 2-propenyl, iota, 2-dimethylpropenyl, j, 2 dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, hexene , 2, hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, decyl-fluorenyl, 2-methyl-1-pentenyl, 3-methyl -丨pentenyl, 4-methyl-oxime-pentenyl, !methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,驭Methyl-2-pentenyl,! _Methyl_3_pentenyl, 2-methyl_3_pentenyl '夂• fluorenyl 3-pentenyl, 4-methyl-3-pentenyl, 1-methyl_4· Pentenyl, 夂•decyl-4-pentenyl, 3-mercapto-4-pentenyl, 4-methyl-4-enopentyl, dimercapto-2-butenyl, U_二Methyl-3-phenylbutenyl, 12-dimethyljbutylene, 1,2-dimethyl-2-butenyl, L2-didecyl-3-butenyl, dimercapto-1- Butenyl, 1,3-dimethyl-2-nitinyl, dimethylene, butenyl, 2,2-dimercapto-3-butenyl, 2,3-dimethyl ·butenyl, 2, 夂151170.doc -13- 201127285 dimethyl-2-butenyl, 2,3·dimethyl-3-butenyl, 3,3·dimethyl-butene Base, 3,3-dimethyl-2-butenyl, ethylidene-fluorenyl-butenyl, anthracene ethyl 2-butenyl, 1-ethyl-3-butenyl, 2-ethyl I-butenyl, 2 ethyl-2-butenyl, 2-ethyl-3-butenyl, anthracene, anthracene, 2-trimethyl-2-propenyl, ethyl-1-methyl _2·propenyl group, 1·ethyl 2·fluorenylpropenyl group, fluorenylethyl 2·methyl-2-propenyl group. Cycloalkenyl group: having 3 to 6, preferably 5 or more carbon rings a member of a monocyclic monounsaturated hydrocarbon group, For example, cyclopentene-丨-yl, cyclopentene-3-yl, cyclohexenyl, 1 hexyl-3-yl, cyclohexyl-4. alkynyl and, for example, alkynyloxy, alkynylamine Alkynyl moiety in the group, fluorenyl-(alkynyl)-fluorenyl-(alkyl)amino group or fluorenyl-(alkynyl)-hydrazine-(alkoxy)amino group: having two or more carbon atoms' For example, 2 to 4, 2 to 6, or 3 to 6 carbon atoms, and a straight or branched bond group having a bond at any position, such as 匚2_(36 fast radicals, such as ethynyl, 1-propynyl , 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-nonyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3- Pentynyl, 4-pentynyl'-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4·hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-indolyl-3-pentynyl, 1-methyl-4-pentynyl, 2-indolyl-3-pentynyl, 2-methyl-4-pentyl group, 3-methyl-1-pentyl group, 3-methyl-4-pentenyl group, 4-methyl-1-decynyl group, 4-mercapto-2 -pentynyl 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl 3-butynyl, 3,3-dimercapto-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butene 151170.doc -14· 201127285 alkynyl, 2-Ethyl-3-butynyl, 1-ethyl-!-▼-yl-2-propynyl. An oxy group, as defined above, which is attached via an oxygen atom, for example, an oxy group, an ethoxy group, a n-propoxy group, an i-methyl ethoxy group, a butoxy group, a methoxy group. , 2-methylpropoxy or ι, ΐ-dimethylethoxy, pentyloxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, ι, ι· dimethylpropoxy, i,2-dimethylpropoxy, 2,2-dimethylpropoxy, ethyl ethoxy, hexyloxy, benzyloxy, 2-methyl Pentyl pentyloxy, 3-methyl methoxyoxy, 4-methylpentyloxy, 1,1-dimethylbutoxy, 1,2-didecylbutoxy, 1,3-dimethylbutyl Oxyl, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, i•ethylbutoxy, 2·ethylbutoxy 1,1,2-trimethylpropoxy, 12 2 -trimethylpropoxy, oxime ethyl-1-mercaptopropoxy or oxime-ethyl-2-methylpropoxy . a 5- or 6-membered heterocyclic ring: a cyclic group having 5 or 6 ring atoms, and a ring, 2, 3 or 4 ring atoms selected from the group consisting of a hetero atom consisting of ruthenium, S and N, wherein the % group The group is saturated, partially unsaturated or aromatic. The compound of formula I contains two pairs of palmar centers and may contain - or a plurality of other pairs of palmar centers depending on the mode of substitution. Thus, the compounds of the invention may exist in the form of the '屯 enantiomer or diastereomer or enantiomer or diastereomeric H. The present invention provides pure enantiomers or diastereomers and mixtures thereof.

R3 蘇型R3 Su type

R3 赤型R3 red

S 151170.doc 201127285 式！化合物亦可能以N_氧化物及/或其農業上適用之⑼ 式存在，鹽之類型通常並不重要。適合鹽通常為彼^離 子之鹽或彼等酸之酸加成鹽，其陽離子及陰離子分㈣化 合物I之除草活性無不利作用。 適合陽離子尤其為鹼金屬（較佳鐘、納或卸）、驗土金屬 (較佳鈣或鎂）及過渡金屬（較佳錳、銅、辞或鐵）之離子。 可使用之另一陽離子為敍，其中， 可經Ci-C：4烷基、羥基_Ci_C4烷基 基、羥基-C1-C4烷氧基烷基 若需要，1至4個氫原子 、Cl，C4院氧基 、苯基或苯甲基置換， 較佳為錄、二甲基録、二異丙基錄、目甲基錢四丁基 銨、2-(2-羥基乙小氧基）乙小基銨、二（2羥基乙小基） 錄、二甲基苯甲基銨。另_適合錄陽離子為式^藉由燒 基化或芳基化而季銨化之吡啶氮原子。亦適合之陽離子為 鱗離子、錡離子，較佳三（Cl_C4烷基）鍍離子，或氧化巯離 子，較佳三（C丨-C4烷基）氧化銃離子。 適合酸加成鹽之陰離子主要為氣離子、溴離子、氟離 子、硫酸氫根、硫酸根、磷酸二氫根、磷酸氫根、硝酸 根、碳酸氫根、碳酸根、六氟矽酸根、六氟磷酸根、笨甲 酸根以及心-匸4烷酸之陰離子，較佳曱酸根、乙酸根、丙 酸根、丁酸根或三氟乙酸根。 就代號而言，中間物之尤佳實施例對應於式基團的 尤佳實施例。 在一特定實施例中’式Ϊ化合物之代號具有以下含義， 151170.doc -16 - 201127285 此等含義獨自且彼此組合為式i化合物之特定實施例： 在式I化合物之一實施例中，下標n之值為〇至3，較佳為 0、1或2’尤其為1。在另一貫施例中，其為〇。若至少一 個基團R存在’則其較佳位於位置3、4及/或5，尤其位置3 或4。若下標η之值為2，則基團R較佳在位置3,5或3,4。 基團R之實施例為齒素，尤其氯或氟。基團R之其他實 施例為氰基或硝基，尤其氰基。 基團Rn之尤佳實施例包括以下：3-F、3,4-F2、3,5-F2、 3,4,5-F3、3-F，4-Cl、4-C1、4-F、3-CN。 基團R1之適宜實施例為氫、Cl_C4烷基、氰基_Ci_C4烷 基、C3-C6烯基、C3-C6炔基、C^-Cs鹵烧基及經取代之2_苯 基。基團R1之較佳實施例為氫；Cl-C：4院基；氰基曱基； 烯丙基；炔丙基；較佳包含1至3個鹵素原子之Ci_C4鹵烷 基；苯基或苯曱基，該等芳族基團可部分或完全經取代。 R1之尤佳實施例包括以下：Η、CH3、C2H5、CH2CN、 CH2C^CH、CH2CH2F、ch2chf2、ch2cf3、ch2och3。 基團R1之進一步尤其較佳實施例為Ci_C4鹵烷基，例如 CH2CH2F、CH2CHF2、CH2CF3、CH2CH2C1、CH2CHC12 及 CH2CC13。 基團R2之適宜實施例為鹵素、氰基、硝基、Ci_C4烷 基、C】-C4烧氧基、S(0)mRbb、NRiRii、Ci_c4鹵烷基、 鹵烷氧基。基團R2之較佳實施例包括鹵素、CN、N〇2、 CH3、CHF2、cf3、ochf2、0Cf3。基團 r2之尤佳實施例 係選自由氟、氣、溴及碘組成之群。尤其較佳地，R2不為S 151170.doc 201127285 style! The compound may also be present as N-oxide and/or its agriculturally applicable formula (9), the type of which is usually not critical. Suitable salts are usually the salt of the ion or the acid addition salt of the acid, and the herbicidal activity of the cation and the anion (IV) compound I is not adverse. Suitable cations are especially alkali metal (preferably clock, nano or unloaded), soiled metal (preferably calcium or magnesium) and transition metal (preferably manganese, copper, rhenium or iron) ions. Another cation which can be used is exemplified by Ci-C: 4 alkyl, hydroxy-Ci_C4 alkyl, hydroxy-C1-C4 alkoxyalkyl, if desired, 1 to 4 hydrogen atoms, Cl, C4, phenyl or benzyl substituted, preferably dimethyl, diisopropyl, methyl butyl tetrabutyl, 2-(2-hydroxyethyloxy) Small base ammonium, bis(2-hydroxyethyl small group), dimethylbenzyl ammonium. Further, it is suitable to record a cation as a pyridine nitrogen atom which is quaternized by alkylation or arylation. Also suitable cations are scaly ions, strontium ions, preferably tris(Cl_C4 alkyl) plated ions, or cerium oxide ions, preferably tris(C丨-C4 alkyl) cerium oxide ions. The anions suitable for acid addition salts are mainly gas ions, bromide ions, fluoride ions, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogencarbonate, carbonate, hexafluoroantimonate, and six. An anion of fluorophosphate, benzethate and heart-anthraquinone, preferably citrate, acetate, propionate, butyrate or trifluoroacetate. In the case of the code, a preferred embodiment of the intermediate corresponds to a preferred embodiment of the formula. In a particular embodiment, the designation of a compound of the formula has the following meanings: 151170.doc -16 - 201127285 Specific meanings of the compounds of the formula i, individually and in combination with each other: In one embodiment of the compound of formula I, The value of the standard n is 〇 to 3, preferably 0, 1 or 2', especially 1. In another embodiment, it is 〇. If at least one of the groups R is present, it is preferably located at positions 3, 4 and/or 5, especially at positions 3 or 4. If the value of the subscript η is 2, the group R is preferably at the position 3, 5 or 3, 4. An example of a group R is a dentate, especially chlorine or fluorine. Other examples of the group R are cyano or nitro, especially cyano. Particularly preferred embodiments of the group Rn include the following: 3-F, 3,4-F2, 3,5-F2, 3,4,5-F3, 3-F,4-Cl, 4-C1, 4-F , 3-CN. Suitable examples of the group R1 are hydrogen, Cl_C4 alkyl, cyano-Ci_C4 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, C^-Cs haloalkyl and substituted 2-phenyl. Preferred examples of the group R1 are hydrogen; Cl-C: 4-yard; cyanoindenyl; allyl; propargyl; Ci_C4 haloalkyl preferably having 1 to 3 halogen atoms; Benzoyl groups, these aromatic groups may be partially or completely substituted. Particularly preferred embodiments of R1 include the following: Η, CH3, C2H5, CH2CN, CH2C^CH, CH2CH2F, ch2chf2, ch2cf3, ch2och3. Further particularly preferred embodiments of the group R1 are Ci_C4 haloalkyl groups such as CH2CH2F, CH2CHF2, CH2CF3, CH2CH2C1, CH2CHC12 and CH2CC13. Suitable examples of the group R2 are halogen, cyano, nitro, Ci_C4 alkyl, C]-C4 alkoxy, S(0)mRbb, NNiRii, Ci_c4 haloalkyl, haloalkoxy. Preferred examples of the group R2 include halogen, CN, N〇2, CH3, CHF2, cf3, ochf2, and OCf3. A preferred embodiment of the group r2 is selected from the group consisting of fluorine, gas, bromine and iodine. Particularly preferably, R2 is not

S 151170.doc -17- 201127285 氯。更尤其較佳地，R2為氟。 某基團：之適宜實施例為自素、氰基、硝基、Cl-c4烷 二丨其4燒氧基、S⑼mRbb、NRlRil、Ci C4***基、c丨A "乳基。基團R3之較佳實施例包括齒素、cn、n02、 CH3 ' CHF2 ' CF3 ' OCHF2 ' 〇CF3 〇 ^ 11 p3 俜選自“ e 2 ui 3 &團汉之較佳實施例 係“由故、a、漠及蛾組成之群。尤其較佳地，R3不為 氯。 更尤其較佳地，R3為氟。 更尤其較佳地，R3為溴 更尤其較佳地，R3為碘。 在較佳式I化合物中，基團R2與R3為不同的。 尤佳為R2與R3之以下組合： 2,5-F2 ； 2-F,5-Cl ； 2-F,5-Br ； 2-F,5-CN ； 2-F55-N〇2 ； 2-F，5-CF3 ; 2-F，5-〇CH3 ; 2-Cl，5-F 〇 此等組合之一個實施例為Rl選自鹵烧基、視情況經取代 之苯甲基或視情況經取代之苯基的式〗化合物。 在較佳式I化合物中，R、…及R3中之至少一個基團為 氟。 尤其就用途而言，較佳為下表中所彙編之式1/(匕合物。 此外，表中針對取代基所提及之基團本質上獨立於提及該 等基團之組合為所討論取代基之尤佳態樣。 表1 式I化合物’其中Rn為H’且在各情況下化合物之r1、r2及 R3之組合對應於表A之一列，但a-26行除外 -18- 151170.doc 201127285 表2 式1化合物，其中Rn為3-CN，且在各情況下化合物之R1、 R2及R3之組合對應於表A之一列 表3 式I化ό物其中Rn為4-C1 ’且在各情況下化合物之ri、r2 及R3之組合對應於表A之一列 表4 式I化&物其中為3-F，且在各情況下化合物之ri、r2 及R之組合對應於表A之一列，但A_丨〇行除外 表5 式I化&物其中Rn為4-F，且在各情況下化合物之Rl、R2 及R之組合對應於表A之一列，但A_丨丨行除外 表6 式I化〇物其中Rn為3,4-F2，且在各情況下化合物之Rl、 R及R3之組合對應於表A之一列，但A_u&A_l2行除外 表7 式I化p物，其中Rn為3,5 F2，且在各情況下化合物之r1、 R2及R3之組合對應於表A之一列 表8 式1化合物’其中Rn為3_F，4-C1，且在各情況下化合物之 R、R及R之組合對應於表A之一列 表9 式I化合物’其中Rn為3 4 5 F3 ’且在各情況下化合物之 R、R及R之組合對應於_表A之一列 151170.doc § 201127285 表A-式I化合物S 151170.doc -17- 201127285 Chlorine. More particularly preferably, R2 is fluorine. A suitable group of examples: self-derived, cyano, nitro, Cl-c4 alkane, bismuth 4, alkoxy, S(9)mRbb, NRlRil, Ci C4, self-calcinating, c丨A "lactyl. Preferred embodiments of the group R3 include dentate, cn, n02, CH3 'CHF2 'CF3 'OCHF2 ' 〇CF3 〇^ 11 p3 俜 selected from "e 2 ui 3 & Therefore, a, desert and moth group. Particularly preferably, R3 is not chlorine. More particularly preferably, R3 is fluorine. More particularly preferably, R3 is bromine. More preferably, R3 is iodine. In a preferred compound of formula I, the groups R2 and R3 are different. More preferably, the combination of R2 and R3 is: 2,5-F2; 2-F, 5-Cl; 2-F, 5-Br; 2-F, 5-CN; 2-F55-N〇2; 2- F,5-CF3; 2-F,5-〇CH3; 2-Cl,5-F 一个 One example of such a combination is that R1 is selected from a halogen group, optionally substituted benzyl or, as the case may be a compound of the formula substituted for phenyl. In a preferred compound of formula I, at least one of R, ... and R3 is fluoro. Particularly in terms of use, it is preferably a formula 1/(complex) as compiled in the following table. Further, the groups mentioned in the table for the substituent are essentially independent of the combination of the groups. A preferred aspect of the substituents is discussed. Table 1 Compounds of formula I wherein Rn is H' and in each case the combination of r1, r2 and R3 of the compound corresponds to one of Table A, except for line a-26--18- 151170.doc 201127285 Table 2 Compound of formula 1, wherein Rn is 3-CN, and in each case the combination of R1, R2 and R3 of the compound corresponds to one of Table A. List 3 Formula I of the formula I wherein Rn is 4-C1 'and in each case the combination of ri, r2 and R3 of the compound corresponds to one of the tables in Table A. The formula <RTI ID=0.0>> In a column of Table A, except for A_丨〇, except that Rn is 4-F, and in each case the combination of R1, R2 and R of the compound corresponds to one of Table A, but A_丨丨Except Table 6 Formula I Chemicals wherein Rn is 3,4-F2, and in each case the combination of R1, R and R3 of the compound corresponds to one of the columns of Table A, but the A_u&A_l2 line exclusion table 7 a compound of p, wherein Rn is 3,5 F2, and in each case the combination of r1, R2 and R3 of the compound corresponds to one of Table A. The compound of formula 1 wherein Rn is 3_F, 4-C1, and The combination of R, R and R of the compound in each case corresponds to one of the compounds of Table A. The compound of formula I wherein Rn is 3 4 5 F3 'and in each case the combination of R, R and R of the compound corresponds to the _ table A column 151170.doc § 201127285 Table A - Compounds of formula I

編號 R1 R2 R3 A-l H F F A-2 H F Cl A-3 H F Br A-4 H F CN A-5 H F N〇2 A-6 H F cf3 A-7 H F och3 A-8 H Cl Cl A-9 H Cl F A-10 ch3 F F A-ll ch3 F Cl A-l 2 ch3 F Br A-l 3 ch3 F CN A-14 ch3 F N〇2 A-15 ch3 F cf3 A-16 ch3 F och3 A-17 ch3 Cl Cl A-l 8 ch3 Cl F A-l 9 C2H5 F F A-20 C2H5 F Cl A-21 C2H5 F Br A-22 C2H5 F CN A-23 C2H5 F N〇2 A-24 C2H5 F cf3 A-25 C2H5 F och3 编號 R1 R2 R3 A-26 c2h5 Cl Cl A-27 C2H5 Cl F A-28 ch2cn F F A-29 ch2cn F Cl A-30 ch2cn F Br A-31 ch2cn F CN A-32 ch2cn F N〇2 A-33 ch2cn F cf3 A-34 ch2cn F och3 A-35 ch2cn Cl Cl A-36 ch2cn Cl F A-37 ch2c=ch F F A-38 ch2och F Cl A-39 ch2och F Br A-40 ch2c=ch F CN A-41 ch2c=ch F N〇2 A-42 ch2c=ch F cf3 A-43 ch2c=ch F och3 A-44 CH2C 三 CH Cl Cl A-45 ch2och Cl F A-46 CH2CH2F F F A-47 CH2CH2F F Cl A-48 CH2CH2F F Br A-49 CH2CH2F F CN A-50 ch2ch2f F N〇2 151170.doc -20- 201127285 編號 R1 R2 R3 A-51 CH2CH2F F cf3 A-52 CH2CH2F F OCH3 A-53 CH2CH2F Cl Cl A-54 CH2CH2F Cl F A-55 CH2CHF2 F F A-56 CH2CHF2 F Cl A-57 CH2CHF2 F Br A-58 CH2CHF2 F CN A-59 CH2CHF2 F N〇2 A-60 CH2CHF2 F cf3 A-61 CH2CHF2 F och3 A-62 CH2CHF2 Cl Cl A-63 CH2CHF2 Cl F A-64 CH2CF3 F F A-65 CH2CF3 F Cl A-66 CH2CF3 F Br A-67 CH2CF3 F CN A-68 ch2cf3 F N〇2 A-69 CH2CF3 F cf3 A-70 CH2CF3 F och3 A-71 CH2CF3 Cl Cl A-72 CH2CF3 Cl F A-73 CH20CH3 F F A-74 CH20CH3 F Cl A-75 CH20CH3 F Br A-76 CH20CH3 F CN A-77 CH20CH3 F N02 A-78 CH20CH3 F cf3 A-79 CH20CH3 F och3 A-80 CH20CH3 Cl Cl A-81 CH20CH3 Cl F A-82 CH2CH2CF3 F F A-83 CH2CH2CF3 F Cl A-84 CH2CH2CF3 F Br 編號 R1 R2 R3 A-85 CH2CH2CF3 F CN A-86 CH2CH2CF3 F N〇2 A-87 CH2CH2CF3 F cf3 A-88 CH2CH2CF3 F och3 A-89 CH2CH2CF3 Cl F A-90 CH2CF2CHF2 F F A-91 CH2CF2CHF2 F Cl A-92 CH2CF2CHF2 F Br A-93 CH2CF2CHF2 F CN A-94 CH2CF2CHF2 F N〇2 A-95 CH2CF2CHF2 F cf3 A-96 ch2cf2chf2 F och3 A-97 CH2CF2CHF2 Cl F A-98 ch2c6h5 F F A-99 ch2c6h5 F Cl A-100 ch2c6h5 F Br A-101 ch2c6h5 F CN A-102 ch2c6h5 F N〇2 A-103 ch2c6h5 F cf3 A-104 ch2c6h5 F och3 A-105 ch2c6h5 Cl F A-106 CH2(2-F-C6H5) F F A-107 CH2(2-F-C6H5) F Cl A-108 CH2(2-F-C6H5) F Br A-109 CH2(2-F-C6H5) F CN A-110 CH2(2-F-C6H5) F N〇2 A-lll CH2(2-F-C6H5) F cf3 A-112 CH2(2-F-C6H5) F och3 A-113 CH2(2-F-C6H5) Cl F A-114 c6h5 F F A-115 c6h5 F Cl A-116 c6h5 F Br A-117 c6h5 F CN A-118 c6h5 F N〇2No. R1 R2 R3 Al HFF A-2 HF Cl A-3 HF Br A-4 HF CN A-5 HFN〇2 A-6 HF cf3 A-7 HF och3 A-8 H Cl Cl A-9 H Cl F A -10 ch3 FF A-ll ch3 F Cl Al 2 ch3 F Br Al 3 ch3 F CN A-14 ch3 FN〇2 A-15 ch3 F cf3 A-16 ch3 F och3 A-17 ch3 Cl Cl Al 8 ch3 Cl F Al 9 C2H5 FF A-20 C2H5 F Cl A-21 C2H5 F Br A-22 C2H5 F CN A-23 C2H5 FN〇2 A-24 C2H5 F cf3 A-25 C2H5 F och3 No. R1 R2 R3 A-26 c2h5 Cl Cl A-27 C2H5 Cl F A-28 ch2cn FF A-29 ch2cn F Cl A-30 ch2cn F Br A-31 ch2cn F CN A-32 ch2cn FN〇2 A-33 ch2cn F cf3 A-34 ch2cn F och3 A-35 ch2cn Cl Cl A-36 ch2cn Cl F A-37 ch2c=ch FF A-38 ch2och F Cl A-39 ch2och F Br A-40 ch2c=ch F CN A-41 ch2c=ch FN〇2 A- 42 ch2c=ch F cf3 A-43 ch2c=ch F och3 A-44 CH2C Tri CH Cl Cl A-45 ch2och Cl F A-46 CH2CH2F FF A-47 CH2CH2F F Cl A-48 CH2CH2F F Br A-49 CH2CH2F F CN A-50 ch2ch2f FN〇2 151170.doc -20- 201127285 No. R1 R2 R3 A-51 CH2CH2F F cf3 A-52 CH2CH2F F OCH3 A-53 CH2CH2F Cl Cl A-54 CH2CH2F Cl F A- 55 CH2CHF2 FF A-56 CH2CHF2 F Cl A-57 CH2CHF2 F Br A-58 CH2CHF2 F CN A-59 CH2CHF2 FN〇2 A-60 CH2CHF2 F cf3 A-61 CH2CHF2 F och3 A-62 CH2CHF2 Cl Cl A-63 CH2CHF2 Cl F A-64 CH2CF3 FF A-65 CH2CF3 F Cl A-66 CH2CF3 F Br A-67 CH2CF3 F CN A-68 ch2cf3 FN〇2 A-69 CH2CF3 F cf3 A-70 CH2CF3 F och3 A-71 CH2CF3 Cl Cl A-72 CH2CF3 Cl F A-73 CH20CH3 FF A-74 CH20CH3 F Cl A-75 CH20CH3 F Br A-76 CH20CH3 F CN A-77 CH20CH3 F N02 A-78 CH20CH3 F cf3 A-79 CH20CH3 F och3 A-80 CH20CH3 Cl Cl A-81 CH20CH3 Cl F A-82 CH2CH2CF3 FF A-83 CH2CH2CF3 F Cl A-84 CH2CH2CF3 F Br No. R1 R2 R3 A-85 CH2CH2CF3 F CN A-86 CH2CH2CF3 FN〇2 A-87 CH2CH2CF3 F cf3 A -88 CH2CH2CF3 F och3 A-89 CH2CH2CF3 Cl F A-90 CH2CF2CHF2 FF A-91 CH2CF2CHF2 F Cl A-92 CH2CF2CHF2 F Br A-93 CH2CF2CHF2 F CN A-94 CH2CF2CHF2 FN〇2 A-95 CH2CF2CHF2 F cf3 A-96 Ch 2 cf 2 2 2 2 2 2 2 2 2 2 2 2 5 F cf3 A-104 ch2c6h5 F och3 A-105 ch2c6h5 Cl F A-106 CH2(2-F-C6H5) FF A-107 CH2(2-F-C6H5) F Cl A-108 CH2(2-F-C6H5 F Br A-109 CH2(2-F-C6H5) F CN A-110 CH2(2-F-C6H5) FN〇2 A-lll CH2(2-F-C6H5) F cf3 A-112 CH2(2- F-C6H5) F och3 A-113 CH2(2-F-C6H5) Cl F A-114 c6h5 FF A-115 c6h5 F Cl A-116 c6h5 F Br A-117 c6h5 F CN A-118 c6h5 FN〇2

S 151170.doc •21 · 201127285 編號 R1 R2 R3 A-119 c6h5 F cf3 A-120 c6h5 F OCH3 A-121 c6h5 Cl F A-122 2-F-C6H4 F F A-123 2-F-QH4 F Cl A-124 2-F-C6H4 F Br A-125 2-F—C0H4 F CN A-126 2-F-C6H4 F N〇2 A-127 2-F-C6H4 F cf3 A-128 2-F-C6H4 F och3 A-129 2-F-C6H4 Cl F A-130 CH(CH3)C6H5 F F A-131 CH(CH3)C6Hs F Cl A-132 CH(CH3)C6H5 F BrS 151170.doc •21 · 201127285 No. R1 R2 R3 A-119 c6h5 F cf3 A-120 c6h5 F OCH3 A-121 c6h5 Cl F A-122 2-F-C6H4 FF A-123 2-F-QH4 F Cl A -124 2-F-C6H4 F Br A-125 2-F-C0H4 F CN A-126 2-F-C6H4 FN〇2 A-127 2-F-C6H4 F cf3 A-128 2-F-C6H4 F och3 A-129 2-F-C6H4 Cl F A-130 CH(CH3)C6H5 FF A-131 CH(CH3)C6Hs F Cl A-132 CH(CH3)C6H5 F Br

編號 R1 R2 R3 A-133 CH(CH3)C6H5 F CN A-134 CH(CH3)C6H5 F N〇2 A-135 CH(CH3)C6H5 F cf3 A-136 CH(CH3)C6H5 F och3 A-137 CH(CH3)C6H5 Cl F A-138 CH(CH3)- (2-F-C6Hs) F F A-139 CH<€H3)- (2-F-C6H5) F Cl A-140 CH(CH3)- (2-F-C6H5) F Br A-141 ch(ch3)· (2-F-C6H5) F CN A-142 CH(CH3)- (2-F-C6H5) F N〇2 A-143 CH(CH3)- (2-F-C6H5) F cf3 A-144 CH(CH3)- (2-F-C6H5) F och3 A-145 CH(CH3)- (2-F-C6H5) Cl F 化合物i及其農業上適用之鹽適合以異構體混合物及純 異構體之形式用作除草劑。其以原樣或適當調配之組合物 形式適用。包含化合物I、尤其其較佳態樣之除草組合物 尤其在高施用率下極有效地控制非作物區之植物。其針對 闊葉雜草及作物（諸如小麥、稻穀、玉米、大豆及棉花）中 之雜草起作用，而不會對作物植物造成任何顯著損傷。此 作用主要在低施用率下觀察到。 視所討論之施用方法而定，化合物I，尤其其較佳態 樣，或包含其之組合物可另外用於大量其他作物植物以去 除不要之植被。適合作物之實例為以下： -22- 151170.doc 201127285 洋蔥（Allium cepa)、鳳梨（Ananas comosus)、花生（Arachis hypogaea)、蘆筍（Asparagus officinalis)、燕麥（Avena sativa)、甜菜屬臭椿（Beta vulgaris spec, altissima)、甜菜 屬蒸菁（Beta vulgaris spec, rapa)、歐洲油菜（Brassica napus var. napus)、蕪菁甘藍（Brassica napus var· napobrassica)、芸苔（Brassica rapa var. silvestris)、甘藍 (Brassica oleracea)、黑芥（Brassica nigra)、中國茶 (Camellia sinensis)、紅花草（Carthamus tinctorius)、美國 薄殼山核桃.(Carya illinoinensis)、檸檬（Citrus limon)、甜 橙（Citrus sinensis)、咖啡樹（Coffea arabica)(中果咖啡 (Coffea canephora)、大果咖啡（Coffea liberica))、胡瓜 (Cucumis sativus)、狗牙根（Cynodon dactylon)、胡蘿蔔 (Daucus carota)、油椰子（Elaeis guineensis)、野草每 (Fragaria vesca)、大豆（Glycine max)、陸地棉（Gossypium hirsutum)(中棉（Gossypium arboreum)、草棉（Gossypium herbaceum)、木棉（Gossypium vitifolium))、向曰葵 (Helianthus annuus)、巴西橡膠樹（Hevea brasiliensis)、大 麥（Hordeum vulgare)、啤酒花（Humulus lupulus)、甘薯 (Ipomoea batatas)、胡桃（Juglans regia)、兵豆（Lens culinaris)、 亞麻（Linum usitatissimum)、番莊 (Lycopersicon lycopersicum)、蘋果屬（Malus spec.)、樹薯 (Manihot esculenta)、紫花苜蓿（Medicago sativa)、芭蕉屬 (Musa spec.)、菸草（Nicotiana tabacum)(黃花菸草 (N.rustica))、油橄欖（Olea europaea)、稻（Oryza sativa)、 151170.doc -23- 201127285 萊豆（Phaseolus lunatus)、菜豆（Phaseolus vulgaris)、歐洲 雲杉（Picea abies)、松屬（Pinus spec.)、阿月泽子（Pistacia vera)、婉豆（Pisum sativum)、歐洲甜櫻桃（Prunus avium)、才兆（Prunus persica)、西洋梨（Pyrus communis)、杏 (Prunus armeniaca)、酸樓桃（Prunus cerasus)、巴旦杏 (Prunus dulcis)及歐洲李（Prunus domestica)、紅醋栗（Ribes sylvestre)、蓖麻（Ricinus communis)、甘嚴（Saccharum officinarum)、黑麥（Secale cereale)、白芬子（Sinapis alba)、馬鈴薯（Solatium tuberosum)、高粱（Sorghum bicolor) (蜀黍（s. vulgare))、可可（Theobroma cacao)、紅三葉草 (Trifolium pratense)、小麥（Triticum aestivum)、黑小麥 (Triticale)、硬粒小麥（Triticum durum)、蠶豆（Vicia faba)、葡萄（Vitis vinifera)、玉蜀黍（Zea mays)。 術語「作物植物j亦包括藉由育種、突變誘發或遺傳工 程改造改變之植物。經遺傳改變之植物為遺傳物質已經以 天然條件下不發生之方式藉由雜交、突變或天然重組（亦 即遺傳資訊重新組裝）而改變的植物。在本文中，通常將 一或多個基因整合於植物之遺傳物質中以改良植物之特 性。No. R1 R2 R3 A-133 CH(CH3)C6H5 F CN A-134 CH(CH3)C6H5 FN〇2 A-135 CH(CH3)C6H5 F cf3 A-136 CH(CH3)C6H5 F och3 A-137 CH( CH3)C6H5 Cl F A-138 CH(CH3)- (2-F-C6Hs) FF A-139 CH<€H3)- (2-F-C6H5) F Cl A-140 CH(CH3)- (2- F-C6H5) F Br A-141 ch(ch3)· (2-F-C6H5) F CN A-142 CH(CH3)- (2-F-C6H5) FN〇2 A-143 CH(CH3)- ( 2-F-C6H5) F cf3 A-144 CH(CH3)- (2-F-C6H5) F och3 A-145 CH(CH3)- (2-F-C6H5) Cl F Compound i and its agricultural application The salts are suitable for use as herbicides in the form of isomer mixtures and pure isomers. It is applied as it is or as a suitably formulated composition. Herbicidal compositions comprising Compound I, especially preferred aspects thereof, are extremely effective in controlling plants in non-crop areas, particularly at high application rates. It acts against weeds in broadleaf weeds and crops such as wheat, rice, corn, soybeans and cotton without causing any significant damage to crop plants. This effect is mainly observed at low application rates. Depending on the method of application in question, Compound I, especially its preferred form, or compositions comprising the same may additionally be used in a wide variety of other crop plants to remove unwanted vegetation. Examples of suitable crops are as follows: -22- 151170.doc 201127285 Onium (Allium cepa), pineapple (Ananas comosus), peanut (Arachis hypogaea), asparagus officinalis, oat (Avena sativa), beet skunk (Beta vulgaris Spec, altissima), Beta vulgaris spec (rapa), Brassica napus var. napus, Brassica napus var napobrassica, Brassica rapa var. silvestris, Brassica Oleracea), Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, coffee tree (Coffea arabica) (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, weeds (Fragaria vesca), soybean (Glycine max), upland cotton (Gossypium hirsutum) (Chinese cotton (Gossypium arboreum), grass cotton Gossypium herbaceum), Gossypium vitifolium, Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec. Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, 151170.doc -23- 201127285 Phaseolus lunatus, Phaseolus vulgaris, European spruce (Picea abies), Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis , Apricot (Prunus armeniaca), Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solatium tuberosum, Sorghum bicolor (s. vulgare), cocoa (Theobroma cacao), Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays. The term "crop plant j also includes plants that have been altered by breeding, mutation induction or genetic engineering. Genetically altered plants are genetically altered by hybridization, mutation or natural recombination (ie, genetically) in a manner that does not occur under natural conditions. Plants that are altered by information reassembly. In this context, one or more genes are typically integrated into the genetic material of a plant to improve the characteristics of the plant.

因此，術語「作物植物」亦包括因育種及遺傳工程改造 而獲得對某些類別之除草劑之耐受性的植物，該等除草劑 諸如羥基苯基丙酮酸二加氧酶（HPPD)抑制劑、乙酿乳酸合 成酶（ALS)抑制劑（諸如磺醯基腺（EP-A-257 993、US 5,013,659)或咪唑淋酮（參見例如US 6,222，100、WO 151170.doc • 24- 201127285 01/82685、WO 00/26390、WO 97/41218、WO 98/02526、 WO 98/02527、WO 04/106529、WO 05/20673、WO 03/14357、 WO 03/13225、WO 03/14356、WO 04/16073))、烯醇式丙 酮酸莽草酸3-磷酸合成酶（EPSPS)抑制劑（諸如草甘膦 (glyphosate)(參見例如WO 92/00377))、.麩醯胺酸合成酶 (GS)抑制劑（諸如固殺草（glufosinate)(參見例如EP-A-242 236、EP-A-242 246))或苯腈（oxynil)除草劑（參見例如US 5,559,024” 已藉助於典型育種法（突變誘發）產生諸多對咪唑啉酮（例 如曱氧味草於（imazamox))具有对受性之作物植物（例如 Clearfield®油菜）。已藉助於遺傳工程改造法產生對草甘膦 或固殺草（以商品名RoundupReady®(草甘膦）及Liberty Link®(固殺草）獲得）具有抗性之的作物植物（諸如大豆、棉 花、玉米、甜菜及油菜）》 因此，術語「作物植物」亦包括藉助於遺傳工程改造產 生一或多種毒素（例如菌株桿菌屬之毒素）的植 物。該等遺傳改變植物所產生之毒素包括例如桿菌屬，尤 其蘇雲金芽抱桿菌（5.仏心/叩化似⑷之殺昆蟲蛋白’諸如 内毒素 CrylAb、CrylAc、CrylF、CrylFa2、Cry2Ab、 Cry3A、Cry3Bbl、Cry9c、Cry34Abl 或 Cry35Abl ;或營養 期殺昆蟲蛋白（VIP)，例如VIP1 ' VIP2、VIP3或VIP3A ; 定殖於線蟲（nematode)之細菌的殺昆蟲蛋白，該等細菌例 如發光桿菌屬（尸spp.)或線蟲共生菌屬 spp.);動物生物體之毒素，例如黃蜂、物蛛 151170.doc -25· 201127285 或蛾毒素；真菌毒素，例如來自鏈黴菌（Streptomycetes); 植物凝集素，例如來自婉豆或大麥；凝集素；蛋白酶抑制 劑，例如胰蛋白酶抑制劑、絲胺酸蛋白酶抑制劑、馬鈴薯 塊莖特異蛋白（patatin)抑制劑、半胱胺酸蛋白酶抑制劑或 木瓜蛋白酶抑制劑；核糖體失活蛋白（RIP)，例如蓖麻毒 素、玉米-RIP、相思豆毒素、絲瓜籽蛋白、沙泊寧 (saporin)或異株腹瀉毒蛋白（bryodin);類固醇代謝酶，例 如3-羥基類固醇氧化酶、脫皮素-IDP糖基轉移酶、膽固醇 氧化酶、蛻皮激素抑制劑或HMG-CoA還原酶；離子通道 阻斷劑，例如鈉通道或#5通道之抑制劑；保幼激素醋酶； 利尿激素受體（異株瀉根毒蛋白（helicokinin)受體）；芪合成 酶、二苯甲基合成酶、殼糖酶及葡聚糖酶。在植物中，此 等毒素亦可能以前毒素、雜交蛋白或已截短或以其他方式 改變之蛋白質形式產生。雜交蛋白之特徵為不同蛋白域之 新穎組合（參見例如WO 2002/015701)。該等毒素或產生此 等毒素之遺傳改變植物之其他實例揭示於EP-A 374 753、 WO 93/007278、WO 95/34656、EP-A 427 529、EP-A 451 878 ' WO 03/018810及WO 03/052073中。產生此等遺傳改 變植物之方法為熟習此項技術者所已知且揭示於例如上述 公開案中。諸多上述毒素賦予產生該等毒素之植物對所有 節肢動物分類類別之害蟲，尤其甲蟲（beetle)(鞘翅目 (Coeleropta)) ' 雙翅目昆蟲（dipteran)(雙翅目（Diptera))及 蝴蝶（butterfly)(鱗翅目（Lepidoptera))及線蟲（線蟲綱 (Nematoda))的对受性。 I51170.doc -26- 201127285 產生一或多種編碼殺昆蟲毒素之基因的遺傳改變植物例 如描述於上述公開案中，且其中一些可購得，諸如 YieldGard®(產生毒素 CrylAb 之玉米變種）、YieldGard® Plus(產生毒素CrylAb及Cry3Bbl之玉米變種）、Starlink® (產生毒素Cry9c之玉米變種）、Herculex® RW(產生毒素 Cry34Abl、Cry35Abl及酶草胺膦-N-乙醯基轉移酶 (phosphinothricin-N-acetyltransferase)[PAT]之玉米變種）； NuCOTN® 33B(產生毒素CrylAc之棉花變種）、Bollgard® I (產生毒素CrylAc之棉花變種）、Bollgard® II(產生毒素 CrylAc及Cry2Ab2之棉花變種）；VIPCOT®(產生VIP毒素之 棉花變種）；NewLeaf®(產生毒素Cry3A之馬鈐薯變種）； Bt-Xtra®、NatureGard®、KnockOut® 、BiteGard®、 Protecta®、Btll(例如 Agrisure® CB)及來自 Syngenta Seeds SAS, France之Bt 176(產生毒素CrylAb及PAT酶之玉米變 種）、來自 Syngenta Seeds SAS, France之 MIR604(產生毒素 Cry3 A之改變形式的玉米變種，參見WO 03/018810)、來自 Monsanto Europe S.A·, Belgium 之 MON 863(產生毒素 Cry3Bbl 之玉米變種）、來自 Monsanto Europe S.A., Belgium之IPC 531(產生毒素CrylAc之改變形式的棉花變 種）及來自 Pioneer Overseas Corporation，Belgium之 1507(產 生毒素Cry IF及PAT酶之玉米變種）。 因此，術語「作物植物」亦包括藉助於遺傳工程改造產 生一或多種對於細菌、病毒或真菌病原體更穩固或具有增 加之抗性的蛋白的植物，該等蛋白諸如病原性相關蛋白Therefore, the term "crop plant" also includes plants that are resistant to certain classes of herbicides due to breeding and genetic engineering, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors. , lactic acid synthase (ALS) inhibitors (such as sulfonyl gland (EP-A-257 993, US 5,013, 659) or imidolone (see for example US 6,222,100, WO 151170.doc • 24- 201127285 01/ 82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/ 16073)), enol pyruvate acid 3-phosphate synthase (EPSPS) inhibitors (such as glyphosate (see for example WO 92/00377)), branide synthase (GS) inhibition Agents such as glufosinate (see for example EP-A-242 236, EP-A-242 246) or oxynil herbicides (see for example US 5,559,024) have been induced by typical breeding methods (mutation induced) Producing a number of crop plants (eg, Clearfield® canola) that are resistant to imidazolinones (eg, imazamox). Crop plants (such as soybeans, cotton) that are resistant to glyphosate or geranium (obtained under the trade names RoundupReady® (glyphosate) and Liberty Link®) have been produced by means of genetic engineering. , corn, sugar beet and canola) Therefore, the term "crop plant" also includes plants that are genetically engineered to produce one or more toxins (eg, toxins of the genus Strains). Toxins produced by such genetically altered plants include, for example, bacilli Genus, especially Bacillus thuringiensis (5. 仏心/叩化like (4) insecticidal protein such as endotoxin CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl, Cry9c, Cry34Abl or Cry35Abl; or vegetative insecticidal protein (VIP), such as VIP1 'VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonized by nematodes, such as the genus Photobacterium (corpus spp.) or the nematode symbiotic genus spp.); animal organisms Toxins, such as wasps, spiders 151170.doc -25· 201127285 or moth toxins; mycotoxins, for example from Streptomycetes; plant lectins, examples From cowpea or barley; lectin; protease inhibitors such as trypsin inhibitors, serine protease inhibitors, potato tuber specific protein (patatin) inhibitors, cysteine protease inhibitors or papain inhibitors; ribose Inactivating protein (RIP), such as ricin, corn-RIP, abrin, loofah, saporin or diarrhea venom (bryodin); steroid metabolism enzymes such as 3-hydroxy steroids Oxidase, ecdysone-IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitor or HMG-CoA reductase; ion channel blocker, such as sodium channel or #5 channel inhibitor; juvenile hormone vinegar; Diuretic hormone receptor (helicokinin receptor); purine synthase, benzhydryl synthase, chitinase and glucanase. In plants, these toxins may also be produced by toxins, hybrid proteins, or proteins that have been truncated or otherwise altered. Hybrid proteins are characterized by novel combinations of different protein domains (see, e.g., WO 2002/015701). Such other toxins or other examples of genetically altered plants which produce such toxins are disclosed in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878 'WO 03/018810 and WO 03/052073. Methods of producing such genetically altered plants are known to those skilled in the art and are disclosed, for example, in the above publication. Many of the above toxins confer on the species producing the toxins pests of all arthropod classification categories, especially beetles (Coeleropta) 'dipteran (Diptera) and butterflies (Diptera) Butterfly) (Lepidoptera) and nematode (Nematoda). I51170.doc -26- 201127285 Genetically altered plants that produce one or more genes encoding insecticidal toxins are described, for example, in the above publication, and some of which are commercially available, such as YieldGard® (a maize variety that produces the toxin CrylAb), YieldGard® Plus (a maize variety producing the toxins CrylAb and Cry3Bbl), Starlink® (a corn variety producing the toxin Cry9c), Herculex® RW (producing the toxin Cry34Abl, Cry35Abl and the enzyme phosphinothricin-N-acetyltransferase (phosphinothricin-N-) Acetyltransferase) [PAT] maize variety); NuCOTN® 33B (cotton variant producing toxin CrylAc), Bollgard® I (cotton variant producing toxin CrylAc), Bollgard® II (cotton variant producing toxin CrylAc and Cry2Ab2); VIPCOT® (Variation of cotton toxins producing VIP toxins); NewLeaf® (variables of horse mash produced by toxin Cry3A); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Btll (eg Agrisure® CB) and from Syngenta Seeds SAS, France's Bt 176 (a maize variety producing the toxin CrylAb and PAT enzymes), MIR604 from Syngenta Seeds SAS, France (producing a toxin Cry3) A modified version of maize variant A, see WO 03/018810), MON 863 from Monsanto Europe SA·, Belgium (a maize variety producing the toxin Cry3Bbl), IPC 531 from Monsanto Europe SA, Belgium (a modified form of the toxin CrylAc) Cotton varieties) and 1507 from Pioneer Overseas Corporation, Belgium (a maize variety that produces the toxin Cry IF and PAT enzymes). Thus, the term "crop plant" also includes plants which, by genetic engineering, produce one or more proteins which are more stable or have increased resistance to bacterial, viral or fungal pathogens, such as pathogenicity-related proteins.

S 151170.doc -27- 201127285 (PR蛋白，參見EP_A 392 225)、抗性蛋白（例如產生來自野 生墨西哥馬鈴薯近緣馬鈴薯（心/⑽⑽的兩 種針對致病疫黴菌（户/^ί叩以介以口則）之抗性基因的 馬鈴薯變種）或T4溶菌酶（例如馬鈐薯栽培變種，其因產生 此蛋白而對細菌（諸如解澱粉歐文氏菌（五 具有抗性）。 因此，術語「作物植物」亦包括可藉助於遺傳工程改造 法改良其生產力之植物，例如提高潛在產量（例如生物質 里、威粒產直·（grain yield)、澱粉、油或蛋白質含量），對 乾旱、鹽或其他限制性環境因素之耐受性或對害蟲及真 函、細函及病毒病原體之抗性。 術m 作物植物」亦包括已藉助於遺傳工程改造法改變 其成份，尤其改良人類或動物飲食的植物，例如產生促進 健康之長鏈ω3脂肪酸或單不飽和ω9脂肪酸的油料植物（例 如Nexera®油菜）。 術語「作物植物」亦包括已藉助於遺傳工程改造法改S 151170.doc -27- 201127285 (PR protein, see EP_A 392 225), resistant proteins (for example, two species of Phytophthora infestans produced from wild Mexican potato close relatives (heart/(10)(10)) a potato variety with a resistance gene) or a T4 lysozyme (for example, a sorghum cultivar, which produces a bacterium against such a protein (such as Erwinia amylovora (five resistant). Therefore, the term "Crop plants" also include plants that can be improved by means of genetic engineering, such as increasing potential yield (eg biomass, grain yield, starch, oil or protein content), for drought, Tolerance of salt or other restrictive environmental factors or resistance to pests and true letters, fine letters and viral pathogens. Surveillance m Crop plants have also included changes in their composition by means of genetic engineering, especially for improving humans or animals. Dietary plants, such as oil-producing plants that produce healthy long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera® canola). The term "crop plants" is also Has been changed by means comprises a genetically engineered method

馬鈴薯）之支鏈澱粉含量。 此外，已發現式I化合物亦適用於植物部分之脫葉及/或Amylopectin content of potato). In addition, it has been found that the compounds of the formula I are also suitable for defoliation of plant parts and/or

或蠶豆之作物植物，特定言之棉花 種使植物乾燥及/或脫葉之組合物， 、油采、向日葵、大豆 。在此方面，已發現一 ’製備此等組合物之方 法及使用式I化合物使植物乾燥及/或脫葉之方法。 式I化合物尤其適用為乾燥劑，使諸如馬鈴薯、油菜 151170.doc -28- 201127285 向曰葵及大丑以及穀類之作物植物之地上部分乾燥。此舉 使得有可能完全機械採收此等重要作物植物。 亦具有經濟利益之處在於使柑橘類水果'撖欖及其他物 種及各種仁果、核果及堅果集中在特定時段内開裂或降低 對樹之黏著’而可能使其便於採收。容易控制之有用植物 (尤其棉花）脫葉亦需要相同機制，亦即促進植物之果實部 分或葉部分與植物之嫩芽部分之間的脫落組織發育。 此外，縮短個別棉花植物成熟之時間間隔，可提高採收 後之纖維品質。 化合物1或包含化合物1之除草組合物可呈例如：現成即 用之喷㈣水溶液、粉末、_減高濃度水性、油性或 其他懸浮液或分散液、乳液、油性分散液、糊狀物、粉 塵'用於撒播之物質’或顆粒，藉助於喷霧、霧化、撒 私政佈、洗灌或處理種子或與種子混合來使用。使用形 式視㈣目的而定；在各情況下’其應儘可能確保本發明 之活性成份最均勻分佈。 该等曲除草組合物包含除草有效量之至少一種式τ化合物 或I之農業上適用之鹽及慣用於調配作物保護劑的助劑。 慣用於調配作物保護劑之助劑的實例為惰性助劑、固體 載劑、界面活性劑（諸如分散劑、保護性膠體、乳化劑、 濕潤劑及增黏劑）、有機及無機增稠劑、殺菌劑、防;東 劑、消泡劑、（若適請色劑及用於種子調配物之 劑。 增稠劑（亦即賦予調 配物改變之流動特性（亦即靜止狀態 151170.doc -29- 201127285 為高黏度及運動狀態為低黏度）的化合物）之實例為多醣， 諸如三仙膠（來自 Kelco 之 Kelzan®)、Rhodopol® 23(Rhone Poulenc)或 Veegum®(來自 R.T. Vanderbilt)，以及有機及無 機層狀礦物，諸如Attaclay®(來自Engelhardt)。 消泡劑之實例為聚矽氧乳液（諸如，Silikon® SRE (Wacker)或來自Rhodia之Rhodorsil®)、長鏈醇、脂肪酸、 脂肪酸鹽、有機氟化合物及其混合物。 可添加殺細囷劑以穩定水性除草調配物。殺細菌劑之實 例為基於雙氣齡及苯甲醇半甲縮酸之殺細菌劑（來自之 Proxel® 或來自 Thor Chemie 之 Acticide® rS及來自 R〇hm &Or a broad-leaved crop plant, specifically a cotton plant that makes the plant dry and/or defoliated, oil, sunflower, soybean. In this regard, a method of preparing such compositions and methods of using the compounds of formula I to dry and/or defoliate plants have been discovered. The compounds of formula I are especially useful as desiccants for partially drying the ground of crop plants such as potato, canola 151170.doc -28- 201127285 to hollyhock and ugly and cereal crops. This makes it possible to completely harvest these important crop plants mechanically. It is also of economic interest to concentrate the citrus fruit 'Ylang and other species and various pome fruits, stone fruits and nuts in a specific period of time to crack or reduce adhesion to the tree' and may make it easier to harvest. The defoliation of useful plants (especially cotton) that are easy to control also requires the same mechanism, i.e., promoting the development of exfoliated tissue between the fruit portion or leaf portion of the plant and the shoot portion of the plant. In addition, shortening the time interval between the ripening of individual cotton plants can improve the fiber quality after harvesting. Compound 1 or the herbicidal composition comprising Compound 1 may be, for example, ready-to-use spray (tetra) aqueous solution, powder, _ reduced concentration aqueous, oily or other suspension or dispersion, emulsion, oily dispersion, paste, dust 'Substances used for spreading' or granules are used by means of spraying, atomizing, smearing, rinsing or treating seeds or mixing with seeds. The use form depends on the purpose of (iv); in each case, it should be as far as possible to ensure the most uniform distribution of the active ingredients of the present invention. The koji herbicidal composition comprises a herbicidally effective amount of at least one agricultural compound of formula τ or I and an adjuvant conventionally used for formulating crop protection agents. Examples of auxiliaries customarily used in the formulation of crop protection agents are inert auxiliaries, solid carriers, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), organic and inorganic thickeners, Fungicides, anti-fouling agents; anti-foaming agents, anti-foaming agents, and agents for seed formulations. Thickeners (that is, the flow characteristics that give the formulation a change (ie, static state 151170.doc -29) - 201127285 is a compound with high viscosity and low viscosity). Polysaccharides such as Sanxian gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from RT Vanderbilt), and organic And inorganic layered minerals such as Attaclay® (from Engelhardt). Examples of antifoaming agents are polyoxynized emulsions (such as Silikon® SRE (Wacker) or Rhodorsil® from Rhodia), long chain alcohols, fatty acids, fatty acid salts, Organofluorine compounds and mixtures thereof. A microbicidal agent can be added to stabilize the aqueous herbicidal formulation. An example of a bactericide is a bactericide based on two-age age and benzyl alcohol hemi-acid (from Proxel® Or Acticide® rS from Thor Chemie and from R〇hm &

Haas之Kathon MK)，以及基於異噻唑啉酮衍生物（諸如烷 基異噻唑啉酮及苯并異噻唑啉酮）之殺細菌劑（來自Th〇rHaas's Kathon MK), and bactericides based on isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (from Th〇r)

Chemie之 Acticide MBS)。 ▼ % 牙、％ "0·〉田 〇 著色劑之貫例為水難溶性顏料及水溶性染料。可提及 實例為已知以下名稱之染料：若丹明（RhGdamin)B、c丄 料紅112及C_L溶劑紅卜以及顏料藍15:4、顏料藍15:3、 料藍15·2、顏料藍15:1、顏料藍⑽、顏料黃1、顏料黃^ 顏料紅112、顏料紅48:2、顏 ,颂科紅48:1、顏料紅57:1、顏i ”工53:1、顏料撥43、顏艇於u . ^卜顏料燈5、顏㈣36^ ' 顏枓白6、顏料棕25、驗神答1Λ έτ ,,紙鹼性紫10、驗性紫49、酸Ί ，-工51、酸性紅52、酸 ,1Λ 性1酸性藍9、酸性黃23、鹼十 ，·工10、驗性紅1 〇 8。 、 聚乙酸乙烯醋、聚 黏著劑之實例為聚 乙烯基吡咯啶_ 15I170.doc 5 •30- 201127285 乙烯醇及甲基纖維素（tylose)。 適合惰性助劑為例如以下： 中等沸點至局沸點之礦物油餾份，諸如煤油及柴油；此 外煤焦油及植物或動物來源之油；脂族、環狀及芳族烴， 例如石壤、四氫萘、烧基化茶及其衍生物、烧基化苯及其 衍生物；醇，諸如甲醇、乙醇、丙醇、丁醇及環己醇； 酮，諸如環己酮；或強極性溶劑，例如胺（諸如N_曱基吡 咯啶酮）及水。 固體載劑為礦物土，諸如矽石、矽膠、矽酸鹽、滑石、 兩嶺土、石灰石、石灰，白堊、紅玄武土黃土黏土、 白雲石、石夕藻土、硫酸鈣、硫酸鎂及氧化鎂；經研磨之合 成材料；肥料，諸如硫酸銨、磷酸銨、硝酸銨及尿素；及 植物來源之產品’諸如榖粉 '樹皮粉、木粉及堅果殼粉、 纖維素粉；或其他固體載劑。 適合界面活性劑（佐劑、濕潤劑、增黏劑、分散劑以及 乳化劑）為芳族磺酸（例如木質磺酸（例如B〇rrespers型，Chemie's Acticide MBS). ▼ %牙,% "0·〉田〇 The examples of colorants are water-insoluble pigments and water-soluble dyes. Mention may be made, by way of example, of dyes known under the following names: RhGdamin B, c-red material 112 and C_L solvent red and pigment blue 15:4, pigment blue 15:3, material blue 15.2, pigment Blue 15:1, Pigment Blue (10), Pigment Yellow 1, Pigment Yellow^ Pigment Red 112, Pigment Red 48:2, Yan, Yankehong 48:1, Pigment Red 57:1, Yan i "Work 53:1, Pigment Dial 43, Yan Yu Yu u. ^ Bu paint lamp 5, Yan (four) 36 ^ ' Yan Yanbai 6, pigment brown 25, test God answer 1Λ έτ,, paper alkaline purple 10, test purple 49, sour, work 51, acid red 52, acid, 1 Λ 1 acid blue 9, acid yellow 23, alkali 10, · work 10, test red 1 〇 8., polyvinyl acetate vinegar, polygloc agent example is polyvinylpyrrolidine _ 15I170.doc 5 •30- 201127285 Vinyl alcohol and methyl cellulose (tylose) Suitable inert additives are for example: medium to primary boiling point mineral oil fractions such as kerosene and diesel; in addition to coal tar and plants or Oils of animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as rocky soil, tetrahydronaphthalene, alkylated tea and its derivatives, alkylated benzene and its derivatives; alcohols such as methanol, ethanol, C Butanol and cyclohexanol; ketones, such as cyclohexanone; or strongly polar solvents such as amines (such as N-decylpyrrolidone) and water. Solid carriers are mineral soils such as vermiculite, tannin, tannin Salt, talc, shale, limestone, lime, chalk, red basalt loess clay, dolomite, shixia, calcium sulphate, magnesium sulphate and magnesium oxide; ground synthetic material; fertilizer, such as ammonium sulfate, phosphoric acid Ammonium, ammonium nitrate and urea; and plant-derived products such as barley powder, wood flour and nut shell powder, cellulose powder; or other solid carrier. Suitable for surfactants (adjuvant, wetting agent, viscosity-increasing) Agents, dispersants and emulsifiers) are aromatic sulfonic acids (for example, lignosulfonic acid (for example, B〇rrespers type,

Borregaard)、本盼磺酸、萘續酸（M〇rwet型，Akzo Nobel) 及二丁基萘磺酸（Nekal型，BASF SE))及脂肪酸之鹼金屬 鹽、驗土金屬鹽及銨鹽；烷基磺酸鹽及烷基芳基磺酸鹽、 烧基硫酸鹽、月桂基醚硫酸鹽及脂肪酵硫酸鹽；及硫酸化 十六醇、十七醇及十八醇之鹽，以及脂肪醇二酵醚之鹽； 確化萘及其衍生物與曱醛之縮合物；萘或萘磺酸與苯酚及 甲搭之縮合物；聚氧乙烯辛基苯酚醚、乙氧基化異辛基苯 酚、乙氧基化辛基笨酚或乙氧基化壬基苯酚、烷基苯基聚Borregaard), Benpan sulfonic acid, naphthalene acid (M〇rwet type, Akzo Nobel) and dibutylnaphthalene sulfonic acid (Nekal type, BASF SE)) and alkali metal salts, soil test metal salts and ammonium salts of fatty acids; Alkyl sulfonate and alkyl aryl sulfonate, alkyl sulfate, lauryl ether sulfate and fatty acid sulfate; and sulfated cetyl alcohol, heptadecyl alcohol and stearyl alcohol, and fatty alcohol a salt of diethanol ether; a condensate of naphthalene and its derivatives with furfural; a condensate of naphthalene or naphthalenesulfonic acid with phenol and methylate; polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, Ethoxylated octyl phenol or ethoxylated nonyl phenol, alkyl phenyl poly

S 151170.doc -31 - 201127285 乙一醇謎或二丁基苯基聚乙二醇鍵、烧基芳基聚謎醇、異 十三醇、脂肪醇/環氧乙烷縮合物、乙氧基化蓖麻油、聚 氧乙烤炫基謎或聚氧丙稀烧基輕、月桂醇聚乙二醇謎乙酸 酯、山梨糖醇酯、木質素亞硫酸鹽廢液及蛋白質、變性蛋 白質、多醣（例如甲基纖維素）、疏水性改質澱粉、聚乙稀 醇（Mowiol 型，Clariant)、聚羧酸醋（BASF SE，Sokalan 型）、聚烷氧基化物、聚乙烯胺（BASF SE，Lupamine型）、 聚乙烯亞胺（BASF SE，Lupasol型）、聚乙烯基吡咯啶酮及 其共聚物。 可藉由將活性成份與固體載劑一起混合或研磨來製備粉 末、用於撒播之物質及粉塵。 可藉由使活性成份與固體載劑結合來製備顆粒（例如包 覆顆粒、浸潰顆粒及均質顆粒）。 可藉由添加水由乳液濃縮物、懸浮液、糊狀物、可濕潤 粉末或水可分散顆粒製備水性使用形式。為製備乳液、糊 狀物或油性分散液，原樣或溶解於油或溶劑中之式〗或式 之化合物可藉助於濕潤劑、增黏劑、分散劑或乳化劑於水 中均質化。或者’亦可能製備包含活性物質、濕潤劑、增 黏T、分散劑或乳化劑及（若需要）溶劑或油之濃縮物，該 等濃縮物適合於用水稀釋。 即^型製劑中式Ϊ化合物之濃度可在寬範圍内變化。一 ，而言’調配物包含o.ocn重量％至98重量％、較佳〇〇1重 量％至95重量％之至少一種活性化合物。使用純度為 至丨00%、較佳95%至丨〇〇%(根據NMR光譜）之活性化合物。 151170.doc •32· 201127285 本發明之化合物i可例如如下調配： 1 ·用水稀釋之產品 A水溶性漢縮物 將10重量份活性化合物溶解於9 0重量份水或水溶性溶劑 中。可替代地添加濕潤劑或其他佐劑。用水稀釋之後活性 化合物溶解。此得到活性化合物含量為1〇重量％之調配 物。 B可分散濃縮物 在添加10重量份分散劑（例如聚乙烯基吡咯啶酮）下，將 20重量份活性化合物溶解於70重量份環己酮中。用水稀 釋’得到分散液。活性化合物含量為20重量％。 C可乳化濃縮物 在添加十二烧基笨績酸辦及萬麻油乙氧基化物（在各情 況下為5重量份）下’將15重量份活性化合物溶解於75重量 份有機溶劑（例如烷基芳族物）中。用水稀釋得到乳液。調 配物之活性化合物含量為15重量〇/0。 D乳液 在添加十二烷基苯磺酸鈣及莲麻油乙氧基化物（在各情 況下為5重量份）下，將25重量份活性化合物溶解於3 5重量 份有機溶劑（例如烷基芳族物）中。藉助於乳化劑（例如 Ultraturrax)將此混合物引入30重量份水中且使其成為均質 乳液°用水稀釋得到乳液。調配物活性化合物含量為25重 量％。 E懸浮液 151170.doc •33- 201127285 在攪拌型球磨機中，在添加10重量份分散劑及濕潤劑及 70重量份水或有機溶劑下，將2〇重量份活性化合物粉碎， 得到精細活性化合物懸浮液^用水稀釋得到活性化合物之 穩定懸浮液。調配物中之活性化合物含量為2〇重量％。 F水可分散顆粒及水溶性顆粒 在添加50重量份分散劑及濕潤劑下’將5〇重量份活性化 合物精細研磨，且藉助於技術設備（例如擠壓機、噴霧 塔流化床）使其成為水可分散或水溶性顆粒。用水稀釋 得到活性化合物之穩定分散液或溶液。調配物活性^ 含量為5 0重量％。 G水可分散粉末及水溶性粉末 在添加25重量份分散劑、濕潤劑及矽膠下，將75重量份 活性化合物在轉子子研磨機巾研磨1水稀釋得到活 性化合物之穩定分散液或溶液。調配物之活性化合物含量 為75重量％。 Η凝耀·調配物 在球磨機中，將20重量份活性化合物、1〇重量份分散 劑、1重量份膠凝劑及7G重量份水或有機溶劑研磨，得到 精細懸浮液。用水稀釋得到活性化合物含量為2〇重量％之 穩定懸浮液。 2.待在不稀釋下施用之產品 I粉塵 將5重量份活性化合物精細研磨且與％重量份細粉狀高 屬土緊密混合。此得到活性化合物含量為5重量。/。之可撒 151170.doc •34- 201127285 粉粉末。 J 顆粒（GR、FG、GG、MG) 將〇·5重量份活性化合物精細研磨且與99 $重量份載劑締 合。此處，當前方法為擠壓、喷霧乾燥或流化床。此得到 活性化合物含量為〇.5重量％的待在不稀釋下施用之顆粒。 K ULV溶液（UL) 將10重量份活性化合物溶解於90重量份有機溶劑（例如 二甲苯）中。此得到活性化合物含量為10重量％的待在不稀 釋下施用之產品。 化。物I或包含其之除草組合物可在出苗前或出苗後施 用或與作物植物之種子一起施用。亦可能藉由塗覆作物植 物種子（用除草組合物或活性化合物預處理）來施用除草組 合物或活性化合物。若某些作物植物對活性化合物的耐受 性不佳’則可使用以下施用技術，其中藉助於喷霧設備以 一定方式對除草組合物喷霧使得儘可能使其不與敏感性作 物植物之葉子接觸，而活性化合物到達生長在下面之不要 之植被的葉子或裸露土壤表面（直接喷施，繞路到達（post-directed， lay-by)) ° 在另只鉍例中，式I化合物或除草組合物可藉由處理 種子來施用。 種子處理包含基於本發明之式〗化合物或由其製備之組 合物的熟習此項技術者所熟知之基本上所有程序（拌種、 種子包覆、種子撒粉、浸種、種子包膜、種子多層包覆、 種子包嫒、種子滴灌（seed dripping)及種子丸化）。在本文 151170.doc 201127285 中，除草組合物可經稀釋或不稀釋施用。 術語種子包含所有類型之種子，諸如縠粒、籽、果實、 塊莖、插枝及類似$式。纟本文中，#語種子較佳描述穀 粒及杆。 所用種子可為上述有用植物之種子，以及轉殖基因植物 或藉由慣用育種方法獲得之植物之種子。 活性化合物的施用率視控制目標、季節、目標植物及生 長階段而疋為0.001至3.0 kg/ha、較佳0.01至1 〇 性 物質（a.s.)。為處理種子，通常以每1〇〇公斤種子〇〇〇1至1〇 公斤之量使用化合物I。 使用式I化合物與安全劑之組合可能亦為適宜的。安全 劑為防止損傷有用植物或降低對有用植物之損傷而不會實 質上影響式I化合物對不要之植被之除草作用的化合物。 其可在播種之前使用（例如在處理種子時使用或用於插枝 或幼苗）及有用植物出苗之前或之後使用。安全劑及式“匕 合物可同時或順次使用。適合安全劑為例如（喹啉_8-氧基） 乙酸、1-苯基-5-鹵燒基-1"-1，2,4-三《坐-3-甲酸、1-苯基_ 4,5-二氫-5-烧基比 〇坐·3，5-二甲酸、4,5-二氫-5,5-二芳 基-3-異噁唑甲酸、二氣乙醯胺、α_羥亞胺基苯基乙腈、苯 乙酮肟、4,6-二齒-2-苯基嘧啶、Ν-[[4-(胺基羰基）苯基]磺 醯基]-2-苯甲醯胺' l，8-萘二甲酸酐、2-齒-4-(鹵烷基）-5-嗟唾甲酸、硫代磷酸酯及〇_苯基Ν·烷基胺基曱酸酯及其農 業上有用之鹽（且其限制條件為其具有酸官能性）、其農業 上有用之衍生物（諸如酿胺、酯及硫酯）。 151170.doc -36· 201127285 為拓寬活性譜且獲得協同效應，可將式丨化合物與其他 除草或生長調控活性化合物群之諸多代表性物質或與安全 劑混合且聯合施用。適合混合搭配物為例如1)2,4_噻二 唑、1，3,4-噻二唑、醯胺、胺基磷酸及其衍生物、胺基三 唑、笨胺、芳氧基/雜芳氧基烷酸及其衍生物、苯甲酸及 其衍生物、苯并噻二嗪酮、2_(雜芳醯基/芳醯基卜丨^-環己 二酮、雜芳基芳基酮、苯曱基異噁唑啶酮、間_Cf3_苯基 衍生物、胺基甲酸酯、喹啉羧酸及其衍生物、氯乙醯苯 胺、環己烯酮肟醚衍生物、二嗪、二氣丙酸及其衍生物、 二氫笨并咬喃、二氫呋喃·3-酮、二硝基苯胺、二硝基苯 酚、二苯基醚、聯吡啶、函代羧酸及其衍生物、尿素、3_ 苯基尿嘧啶、咪唑、咪唑啉酮、N_苯基_3,4,5,6_四氫鄰苯 二甲醯亞胺H、環氧乙院、苯紛、芳氧基苯氧基丙 酸酯及雜芳氧基苯氧基丙酸酯、苯基乙酸及其衍生物、2_ 苯基丙酸及其衍生物、吡唑、苯基吡唑、噠嗪、吡啶羧酸 及其衍生物、嘧啶基醚、磺醯胺、磺醯基脲、三嗪、三嗪 酮、***啉酮、***羧醯胺、尿嘧啶以及苯基吡唑啉及異 噁唑啉及其衍生物。 、 此外，化合物I可適用於單獨施用或與其他除草劑組合 施用，或亦可與其他作物保護劑，例如與控制害蟲或植2 病原性真菌或細菌之組合物混合而聯合施用。亦受關注的 是與用於緩解營養及微量元素缺乏之礦物鹽溶液的可混 性。亦可添加諸如非植物毒性油及油濃縮物之其他添加 151170.doc -37- 201127285 可與本發明之式i之吡啶化合物組合使用之除草劑的實 例為： bl)來自脂質生物合成抑制劑之群： 亞汰草（alloxydim)、亞汰草鈉鹽（alloxydim-sodium)、丁 苯草酮（butroxydim)、勉草同（clethodim)、快草酸 (clodinafop)、炔草醋（clodinafop-propargyl)、環殺草 (cycloxydim)、赛伏草（cyhalofop)、丁基賽伏草（cyhalofop-butyl)、禾草靈（diclofop)、甲基禾草靈（diclofop-methyl)、 °惡。坐禾草靈（fenoxaprop)、乙基°惡°垒禾草靈（fenoxaprop-ethyl)、精°惡β坐禾草靈（fenoxaprop-P)、精乙基°惡β坐禾草靈 (fenoxaprop-P-ethyl)、伏寄普（fluazifop)、丁基伏寄普 (fluazifop-butyl)、精伏寄普（fluazifop-P)、精丁基伏寄普 (fluazifop-P-butyl)、0比氟氣禾靈（haloxyfop)、甲基0比氟氯 禾靈（haloxyfop-methyl)、精。比氟氣禾靈（haloxyfop-P)、精 甲基0比氟氣禾靈（haloxyfop-P-methyl)、17惡0坐酿草胺 (metamifop)、°坐淋草醋（pinoxaden)、環苯草酮（profoxydim)、 普拔草（propaquizafop)、啥禾靈（quizalofop)、乙基啥禾靈 (quizalofop-ethyl)、喧禾糠酯（quizalofop tefuryl)、精啥禾 靈（quizalofop-P)、精乙基喧禾靈（quizalofop-P-ethyl)、精 啥禾糠酯（quizalofop-P-tefuryl)、西殺草（sethoxydim)、得 殺草（tepraloxydim)、肪草嗣（tralkoxydim)、°夫草黃 (benfuresate)、丁草特（butylate) ' 草滅特（CyCl〇ate)、得拉 本（dalapon)、哌草丹（dimepiperate)、EPTC、戊草丹 (esprocarb)、益覆滅（ethofumesate)、氟丙酸（flupropanate)、 151170.doc • 38 · 201127285 禾草敵（molinate)、坪草丹（orbencarb)、克草猛（pebulate)、 节草丹（prosulfocarb)、TCA、禾草丹（thiobencarb)、仲草 丹（tiocarbazil)、野麥畏（triallate)及滅草猛（vernolate); b2)來自ALS抑制劑之群： 醢0^ 續隆（amidosulfuron)、四 β坐喊續隆（azimsulfuron)、 免速隆（bensulfuron)、甲基免速隆（bensulfuron-methyl)、 雙草越（bispyribac)、雙草醚鈉鹽、氯嘴確隆（chlorimuron)、 乙基氯响續隆（chlorimuron-ethyl)、氣橫隆（chlorsulfuron)、 西速隆（cinosulfuron)、氣醋績草胺（cloransulam)、甲基氯酷 績草胺（eloransulam-methyl)、環續隆（cyclosulfamuron)、 雙氯續草胺（diclosulam) ' 胺苯項隆（ethametsulfuron)、曱 基胺苯績隆（ethametsulfuron-methyl)、亞速隆（ethoxysulfuron)、 伏速隆（flazasulfuron)、雙說績草胺（florasulam)、敦酮續 隆（flucarbazone)、敗酮石黃隆鈉鹽（flucarbazone-sodium)、 氣0比項隆（Hucetosulfuron)、β坐哺續草胺（flumetsulam)、氟 °定鳴確隆（flupyrsulfuron)、曱基氟咬確隆鈉鹽 (flupyrsulfuron-methyl-sodium)、甲醯0^ 續隆（foramsulfuron)、 氣0比嘴項隆（halosulfuron)、曱基氯0比喷確隆（halosulfuron-methyl)、咪草酸（imazamethabenz) 、ϋ米草酸曱醋 (imazamethabenz-methyl)、曱氧w米草於、曱0米0坐於酸 (imazapic)、依滅草（imazapyr)、滅草啥（imazaquin)、c米草 終（imazethapyr)、依速隆（imazosulfuron)、峨續隆 (iodosulfuron)、甲基蛾確隆鈉鹽（iodosulfuron-methyl-sodium)、甲基二續隆（mesosulfuron)、續草0坐胺（metosulam)、 151170.doc -39- 201127285 甲續隆（metsulfuron)、甲基甲續隆（metsulfuron-methyl)、 於喷確隆（nicosulfuron)、笨胺項隆（orthosulfamuron)、 環氧嘴續隆（oxasulfuron)、五氟續草胺（penoxsulam)、氟嘴 續隆（primisulfuron)、甲基氟嘴續隆（primisulfuron-methyl)、 丙苯續隆（propoxycarbazone)、 丙苯續隆納鹽 (propoxycarbazone-sodium) > 氟橫隆（prosulfuron)、百速隆 (pyrazosulfuron)、乙基百速隆（pyrazosulfuron-ethyl)、痛 咬將草醚（pyribenzoxim)、嘴沙泛（pyrimisulfan)、環醋草 謎（pyriftalid)、嘴草喊（pyriminobac)、甲基嘴草醚 (pyriminobac-methyl)、嘴草硫 _ (pyrithiobac)、嘴草硫喊 納鹽（pyrithiobac-sodium)、甲氧績草胺（pyroxsulam)、玉 响續隆（rimsulfuron)、嘴續隆（sulfometuron)、甲嘴橫隆 (sulfometuron-methyl)、續酿續隆（sulfosulfuron)、售吩卡 巴月宗（thiencarbazone)、甲基嗟吩卡巴膝（thiencarbazone-methyl)、嗟吩績隆（thifensulfuron)、曱基嗟吩續隆 (thifensulfuron-methyl)、縫苯續隆（triasulfuron)、苯橫隆 (tribenuron)、甲基苯項隆（tribenuron-methyl)、三氟咬績 隆（trifloxysulfuron)、氟胺續隆（triflusulfuron)、曱基氟胺 續隆（triflusulfuron-methyl)及三氟甲橫隆（tritosulfuron); b3)來自光合作用抑制劑之群： 莠滅淨（ametryn)、胺。坐草酮（amicarbazone)、草脫淨 (atrazine)、本達隆（bentazone)、本達隆納、克草（bromacil)、 溴酚肟（bromofenoxim)、溴苯腈（bromoxynil)及其鹽及酯、 氣漠隆（chlorbromuron)、殺草敏（chloridazone)、綠麥隆 151170.doc -40- 201127285 (chlorotoluron)、枯草隆（chloroxuron)、氰乃淨（cyanazine)、 甜菜安（desmedipham)、歒草淨（desmetryn)、σ惡哇隆 (dimefuron)、異戊乙淨（dimethametryn)、敵草快（diquat)、 二溴敵草快（diquat-dibromide)、敵草隆（diuron)、伏草隆 (fluometuron)、環。秦酮（hexazinone)、填苯腈（i.oxynil)及其 鹽及其S旨、異丙隆（isoproturon)、愛速隆（isouron)、特胺 靈（karbutilate)、環草定（lenacil)、利穀隆（linuron)、苯嗓 草酮（metamitron)、甲苯0塞隆（methabenzthiazuron)、0比喃 隆（metobenzuron)、曱氧隆（metoxuron)、滅必淨 (metribuzin)、綠榖隆（monolinuron)、草不隆（neburon) ' 百 草枯（paraquat)、二氯百草枯（paraquat-dichloride)、二曱硫 酸百草枯（paraquat-dimetilsulfate)、 甲氯酿草胺 (pentanochlor)、甜菜寧（phenmedipham)、乙基甜菜寧 (phenmedipham-ethyl)、撲滅通（prometon)、撲草淨 (prometryn)、除草靈（propanil)、撲滅津（propazine)、比達 伏（pyridafol)、建草特（pyridate)、環草隆（siduron)、西瑪 津（simazine)、西草津（simetryn)、丁嘆隆（tebuthiuron)、特 草定（terbacil)、特丁通（terbumeton)、特丁津（fgrbuthylazine)、 特丁淨（terbutryn)、嗟苯隆（thidiazuron)及草達津 (trietazine); b4)來自原卟啉原-IX氧化酶抑制劑之群： 亞喜芬（acifluorfen)、亞喜芬鈉鹽（acifluorfen-sodium)、 草芬定（azafenidin)、本卡巴膝（bencarbazone)、雙苯喊草 酮（benzfendizone)、必芬諾（bifenox)、氟丙〇密草醋 151170.doc -41 - 201127285S 151170.doc -31 - 201127285 Ethyl alcohol or dibutyl phenyl polyethylene glycol bond, aryl aryl alcohol, isotridecyl alcohol, fatty alcohol / ethylene oxide condensate, ethoxylation Castor oil, polyoxyethylene bake ray or polyoxypropylene light base, lauryl polyethylene glycol mystery acetate, sorbitol ester, lignin sulfite waste liquid and protein, denatured protein, polysaccharide ( For example, methyl cellulose), hydrophobic modified starch, polyethylene glycol (Mowiol type, Clariant), polycarboxylate (BASF SE, Sokalan type), polyalkoxylate, polyvinylamine (BASF SE, Lupamine) Type), polyethyleneimine (BASF SE, Lupasol type), polyvinylpyrrolidone and copolymers thereof. The powder, the substance for spreading, and the dust can be prepared by mixing or grinding the active ingredient with a solid carrier. Granules (e.g., coated particles, impregnated particles, and homogeneous particles) can be prepared by combining the active ingredient with a solid carrier. Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by the addition of water. For the preparation of emulsions, pastes or oily dispersions, the compounds of the formula or formula which are as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. Alternatively, it is also possible to prepare concentrates containing active substances, wetting agents, tackifying T, dispersing or emulsifying agents and, if desired, solvents or oils, which are suitable for dilution with water. That is, the concentration of the hydrazine compound in the preparation can be varied within a wide range. I. The formulation comprises o.ocn by weight to 98% by weight, preferably from 1% to 95% by weight, of at least one active compound. The active compound is used in a purity of from 00%, preferably from 95% to 丨〇〇% (according to NMR spectrum). 151170.doc • 32· 201127285 The compound i of the present invention can be formulated, for example, as follows: 1 • A product diluted with water A A water-soluble condensate 10 parts by weight of the active compound are dissolved in 90 parts by weight of water or a water-soluble solvent. Wetting agents or other adjuvants may alternatively be added. The active compound is dissolved after dilution with water. This gave a formulation having an active compound content of 1% by weight. B Dispersible Concentrate 20 parts by weight of the active compound are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersing agent such as polyvinylpyrrolidone. The dispersion was obtained by diluting with water. The active compound content was 20% by weight. The C emulsifiable concentrate is prepared by dissolving 15 parts by weight of the active compound in 75 parts by weight of an organic solvent (for example, an alkane) under the addition of a twelfth base acid and an ethoxylate ethoxylate (in each case 5 parts by weight). In the base aromatics). Dilute with water to give an emulsion. The active compound content of the formulation was 15% 〇/0. D Emulsion In the addition of calcium dodecylbenzenesulfonate and a lotus oil ethoxylate (in each case 5 parts by weight), 25 parts by weight of the active compound are dissolved in 35 parts by weight of an organic solvent (eg alkyl aryl) In the family). This mixture was introduced into 30 parts by weight of water by means of an emulsifier (e.g., Ultraturrax) and made into a homogeneous emulsion. The emulsion was diluted with water to give an emulsion. The content of the active compound of the formulation was 25 wt%. E suspension 151170.doc •33- 201127285 In a stirred ball mill, 2 parts by weight of the active compound is pulverized under the addition of 10 parts by weight of a dispersant and wetting agent and 70 parts by weight of water or an organic solvent to obtain a fine active compound suspension. The liquid is diluted with water to give a stable suspension of the active compound. The active compound content in the formulation is 2% by weight. The F water dispersible granules and the water-soluble granules are finely ground with 5 parts by weight of the active compound by adding 50 parts by weight of a dispersing agent and a wetting agent, and are made by means of technical equipment (for example, an extruder, a spray tower fluidized bed) Become water dispersible or water soluble particles. Dilution with water gives a stable dispersion or solution of the active compound. The activity of the formulation was 50% by weight. G Water-Dispersible Powder and Water-Soluble Powder 75 parts by weight of the active compound is diluted with water in a rotor-grinding towel by adding 25 parts by weight of a dispersing agent, a wetting agent and a silicone to obtain a stable dispersion or solution of the active compound. The active compound content of the formulation was 75% by weight. ΗCondensation and Formulation In a ball mill, 20 parts by weight of the active compound, 1 part by weight of a dispersant, 1 part by weight of a gelling agent, and 7 parts by weight of water or an organic solvent are ground to obtain a fine suspension. Dilution with water gives a stable suspension having an active compound content of 2% by weight. 2. Products to be applied without dilution I Dust 5 parts by weight of the active compound are finely ground and intimately mixed with % by weight of fine powdery high genus. This gave an active compound content of 5 parts by weight. /. Can be 151170.doc •34- 201127285 powder powder. J particles (GR, FG, GG, MG) 5 parts by weight of the active compound are finely ground and associated with 99 parts by weight of the carrier. Here, the current method is extrusion, spray drying or fluidized bed. This gave granules of the active compound in an amount of 5% by weight to be applied without dilution. K ULV solution (UL) 10 parts by weight of the active compound are dissolved in 90 parts by weight of an organic solvent such as xylene. This gave a product to be applied without dilution at an active compound content of 10% by weight. Chemical. The herbicidal composition I or the herbicidal composition comprising the same may be applied before or after emergence or with the seeds of the crop plant. It is also possible to apply the herbicidal composition or active compound by coating crop plant seeds (pretreated with a herbicidal composition or active compound). If some crop plants are not well tolerated by the active compound, the following application techniques can be used, wherein the herbicidal composition is sprayed in a manner by means of a spray device so as not to be as close as possible to the leaves of the susceptible crop plants Contact, and the active compound reaches the surface of the leaf or bare soil that grows underneath the unwanted vegetation (post-directed, lay-by) ° In another example, the compound of formula I or weeding The composition can be administered by treating the seed. Seed treatment comprises substantially all of the procedures well known to those skilled in the art based on the compounds of the present invention or compositions prepared therefrom (seed dressing, seed coating, seed dusting, seed soaking, seed coating, seed multi-layer) Coating, seed coating, seed dripping and seed pelleting). In the 151170.doc 201127285, the herbicidal compositions can be applied diluted or undiluted. The term seed encompasses all types of seeds, such as sorghum, seeds, fruits, tubers, cuttings, and the like. In this paper, the #语籽 preferably describes the grain and the rod. The seed to be used may be a seed of the above useful plant, and a seed of a plant which is obtained by a transgenic plant or a conventional breeding method. The application rate of the active compound is 0.001 to 3.0 kg/ha, preferably 0.01 to 1 〇 substance (a.s.) depending on the control target, season, target plant and growth stage. For the treatment of the seed, the compound I is usually used in an amount of from 1 to 1 kg per 1 kg of seed. Combinations of a compound of formula I with a safener may also be suitable. A safener is a compound that prevents damage to useful plants or reduces damage to useful plants without substantially affecting the herbicidal action of the compound of formula I on unwanted vegetation. It can be used before sowing (for example when used in the treatment of seeds or for cuttings or seedlings) and before or after emergence of useful plants. The safener and the formula "the compound can be used simultaneously or sequentially. Suitable safeners are, for example, (quinoline-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1"-1,2,4- 3. "Sit-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl is more than 3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl- 3-isoxazolecarboxylic acid, dioxetamine, α-hydroxyiminophenylacetonitrile, acetophenone oxime, 4,6-didentate-2-phenylpyrimidine, Ν-[[4-(amino group) Carbonyl)phenyl]sulfonyl]-2-benzamide> 1,8-naphthalic anhydride, 2-dentate-4-(haloalkyl)-5-indolecarboxylic acid, phosphorothioate and hydrazine _Phenylindole·alkylamino decanoate and its agriculturally useful salts (and which are limited in their ability to have acid functionality), their agriculturally useful derivatives such as the amines, esters and thioesters. 151170.doc -36· 201127285 To broaden the spectrum of activity and achieve a synergistic effect, a compound of the formula can be mixed with a plurality of representative substances of other herbicidal or growth-regulating active compound groups or with a safener and applied in combination. 1) 2,4_thiadiazole, 1,3,4-thiadiazole, decylamine, aminophosphoric acid and its derivatives, amine Triazole, stupid amine, aryloxy/heteroaryloxyalkanoic acid and its derivatives, benzoic acid and its derivatives, benzothiadiazinone, 2_(heteroaryl fluorenyl/aryl sulfhydryl) Cyclohexanedione, heteroaryl aryl ketone, phenylmeridazolidinone, m-Cf3_phenyl derivative, urethane, quinolinecarboxylic acid and its derivatives, chloroacetanilide, Cyclohexenone oxime ether derivative, diazine, dipropionic acid and its derivatives, dihydro benzoate, dihydrofuran-3-ketone, dinitroaniline, dinitrophenol, diphenyl ether , bipyridine, functional carboxylic acid and its derivatives, urea, 3-phenyl uracil, imidazole, imidazolinone, N_phenyl_3,4,5,6-tetrahydrophthalimide H , Ethylene oxide, benzophenone, aryloxyphenoxypropionate and heteroaryloxyphenoxypropionate, phenylacetic acid and its derivatives, 2_phenylpropionic acid and its derivatives, pyrazole , phenylpyrazole, pyridazine, pyridinecarboxylic acid and its derivatives, pyrimidinyl ether, sulfonamide, sulfonyl urea, triazine, triazinone, triazolinone, triazole carboxamide, uracil And phenylpyrazoline and isoxazoline and derivatives thereof. In addition, Compound I may be suitable for administration alone or in combination with other herbicides, or may be administered in combination with other crop protection agents, for example, in combination with a pest control or plant 2 pathogenic fungus or bacteria. It is miscible with mineral salt solution for relieving nutrient and trace element deficiency. Other additions such as non-phytotoxic oil and oil concentrate can also be added. 151170.doc -37- 201127285 can be combined with the pyridine of formula i of the present invention. Examples of herbicides used in combination with compounds are: bl) from lipid biosynthesis inhibitors: alloxydim, alloxydim-sodium, butyroxydim, valerian (clethodim), clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop , methyl clomazone (diclofop-methyl), ° evil. Sitting on fenoxaprop, ethoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P, fenoxaprop- P-ethyl), fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, 0-fluoro Haloxyfop, methyl 0 is lower than haloxyfop-methyl, fine. Haloxyfop-P, haloxyfop-P-methyl, 17 methacetamide, pinoxaden, benzene Profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop tefuryl, quizalofop-P, Quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tramkoxydim, ° Benfuresate, butarate 'CyCl〇ate', dalapon, dimepiperate, EPTC, esprocarb, ethofumesate , flupropanate, 151170.doc • 38 · 201127285 grass, mollusc, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb ), tiocarbazil, triallate, and vernolate; b2) from ALS inhibitors: 0^ Continuation (amidosulfuron), four-beta squat (azimsulfuron), bensulfuron, bensulfuron-methyl, bispyribac, bispyribac sodium, chlorine Chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam, methyl chlorhexidine Erolansulam-methyl), cyclosulfamuron, diclosulam 'ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, volts Flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, humectosulfuron, beta sulphate Flumetsulam, flupyrsulfuron, flupyrsulfuron-methyl-sodium, forasulfuron, halosulfuron, halosulfuron, Mercapto chloride 0 is better than halosulfuron-methyl Acid (imazamethabenz), imazamethabenz-methyl, 曱 w w rice grass, 曱 0 m 0 sit in acid (imazapic), imazapyr (imazapyr), imazaquin (imazaquin), c rice Imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, chlorpyrifos Metosulam), 151170.doc -39- 201127285 metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, epoxy mouth swell Oxasulfuron), penoxsulam, primisulfuron, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium > prosulfuron, pyrazooururon, pyrazoosulfuron-ethyl, pyridylxim, pyrimisulfan, pyrifalid ), mouth shouting (pyriminobac), methyl-mouth ether (pyri Minobac-methyl), pyrithiobac, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, armor Sulfometuron-methyl, sulfosulfuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thiophene thiophene Thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron , triflusulfuron-methyl and tritosulfuron; b3) from photosynthesis inhibitors: ametryn, amine. Amicarbazone, atrazine, bentazone, bundacron, bromacil, bromofenoxim, bromoxynil and its salts and esters , chlorbromuron, chloridazone, chloroplast 151170.doc -40- 201127285 (chlorotoluron), chloroxuron, cyanazine, desmedipham, valerian Desmetryn, dimefuron, dimethametryn, diquat, diquat-dibromide, diuron, valerulone Fluometuron), ring. Hexazinone, i. oxynil and its salts, and its purpose, isoproturon, isouron, karbutilate, lenacil, Linuron, metamitron, methabenzthiazuron, metobenzuron, metaxuron, metribuzin, monolinuron ), neburon 'paraquat, paraquat-dichloride, paraquat-dimetilsulfate, pentanochlor, phenmedipham , phenmedipham-ethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, Siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, fgrbuthylazine, terding (terbutryn), thidiazuron and cheddar (t Rietazine); b4) from the group of protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone , benzfendizone, bifenox, flubendiacetate vinegar 151170.doc -41 - 201127285

(butafenacil)、克繁草（carfentrazone)、乙基克繁草 (carfentrazone-ethyl)、曱氧基護榖（chlomethoxyfen)、吲。朵 酮草酯（cinidon-ethyl)、異丙η比草酯（fluaz〇iate)、氟嗟。秦草 酯（flufenpyr)、乙基氟噠嗪草酯（flufenpyr-ethyl)、氟烯草 酸（flumiclorac)、戊基氟烯草酸（flumiclorac-pentyl)、丙炔 氟草胺（flumioxazin)、乙羧氟草醚（fluor〇glyCOfen)、乙基 乙缓氟草謎（fluoroglycofen-ethyl)、健草氟（fluthiacet)、甲 基噠草氟（fluthiacet-methyl)、氟磺胺草醚（fomesafen)、鹵 賽芬（halosafen)、乳氟禾草靈（lact0fen)、丙炔噁草_ (oxadiargyl)、樂滅草（oxadiazon) ' 複祿芬（oxyfluorfen)、 環戊噁草酮（pentoxazone)、氟唑草胺（profiuaz〇i)、雙唑草 腈（pyraclonil)、吡草醚（pyrafiufen)、乙基吡草醚 (pyraflufen-ethyl)、嘧啶肟草醚（safiufenacil)、甲磺草胺 (sulfentrazone)、噻二唑草胺（thidiazimin)、2_氯_5-[3 6·二 氫-3-甲基-2,6-二側氧基-4-(三氟曱基）-1(2丑)-嘧啶基]-4-氟-N-[(異丙基）甲基胺磺醯基]苯甲醯胺（B] ; CAS 372137-35-4)、[3-[2-氣-4-氟-5-(1-甲基-6-三氟曱基-2,4-二 側氧基-1，2,3,4-四氫嘧啶-3-基）苯氧基]·2-α比啶氧基]乙酸乙 酯（B_2 ; CAS 353292-31-6)、Ν-乙基-3-(2,6-二氣-4-三氟曱 基苯氧基）-5-甲基-lif-吡唑-l曱醯胺（B_3 ; CAS 452098-92-9)、N-四氫呋喃曱基·3·(26_二氣_4三氟曱基苯氧基）_ 5-甲基-1//-吡唑-1-甲醯胺（B—4 ; cas 915396-43-9)、Ν-乙 基-3-(2-氯-6-氟-4-三氟甲基苯氧基）_5曱基丨丑。比唑·卜甲 醯胺（Β·5 ; CAS 452099-05-7)及N-四氫呋喃甲基-3-(2-氯- I5H70.doc • 42· 201127285 6-氟-4-三氟甲基苯氧基）-5-甲基-1//-吡唑-1-曱醯胺（B-6 ; CAS 452100-03-7); b5)來自漂白劑除草劑之群： 苯草謎（aclonifen)、殺草強（amitrol)、氟丁酿草胺 (beflubutamid)、苯并雙環酮（benzobicyclon)、吡草酮 (benzofenap)、異噁草酮（cl〇mazone)、吡氟草胺（diflufenican)、 氟啶草酮（fluridone)、氟咯草酮（flurochloridone)、呋草酮 (flurtamone)、異噁唑草酮（isoxanut〇le)、曱基磺草酮 (mesotrione)、達草滅（norflurazon)、氟吼醢草胺（pic〇iinafen)、 口比崎托利（pyrasulfutole)、节草 °坐（pyrazolynate)、普芬草 (pyrazoxyfen)、磺草酮（sulc〇tri〇ne)、特伏曲酮(tefuryltrione)、 特波曲酮（tembotrione)、托拉美膝（topramezone)、4-經 基-3-[[2-[(2-曱氧基乙氧基）曱基]-6-(三氟曱基）-3-。比啶基] 羰基]雙環[3.2.1]辛-3-烯-2-酮（B-7; CAS 352010-68-5)及 4-(3-三氟甲基笨氧基）-2-(4-三氟甲基苯基）嘧啶（B-8 ; CAS 180608-33-7)； b6)來自EPSP合成酶抑制劑之群： 草甘膦、草甘膦-異丙銨及草甘膦-三曱基锍（草硫膦 (sulfosate)); b7)來自麩醯胺酸合成酶抑制劑之群： 广 畢拉草（bilanaphos或bialaphos))、畢拉草鈉、固殺草及 固殺草銨鹽； b8)來自DHP合成酶抑制劑之群： 項草靈（asulam); 5 151170.doc -43- 201127285 b9)來自有絲***抑制劑之群： 胺草鱗（amiprophos)、曱基胺草碟（amiprophos-methyl)、 氟草胺（benfluralin)、抑草璃（butamiphos)、比達寧 (butralin)、卡草胺（carbetamide)、氣苯胺靈（chlorpropham)、 敵草索（chlorthal)、二甲基敵草索（chlorthal-dimethyl)、撻 乃安（dinitramine)、氟硫草定（dithiopyr)、乙丁稀氟靈 (ethalfluralin)、氟硝草（fluchloralin)、消草續靈（oryzalin)、 施得圃（pendimethalin)、胺氟樂靈（prodiamine)、苯胺靈 (propham)、炔苯酿草胺（propyzamide)、牧草胺（tebutam)、 嘆草咬（thiazopyr)及三福林（trifluralin); blO)來自VLCFA抑制劑之群： 乙草胺（acetochlor)、拉草（alachlor)、莎稗填（anilofos)、 丁 基拉草（butachlor)、唾草胺（cafenstrole)、二甲草胺 (dimethachlor)、汰草滅（dimethanamid)、精汰草滅 (dimethenamid-P)、大芬滅（diphenamid)、四0坐酸草胺 (fentrazamide)、氟售草胺（flufenacet)、滅芬草（mefenacet)、 滅草胺（metazachlor)、莫多草（metolachlor)、左旋莫多草 (metolachlor-S)、萘丙胺（naproanilide)、滅落脫（napropamide)、 稀草胺（pethoxamid)、派草鱗（piperophos)、丙草胺 (pretilachlor)、雷蒙得（propachlor)、異丙草胺（propisochlor)、 普羅蘇芬（pyroxasulfone)(KIH-485)及欣克草（thenylchlor); 式2化合物：(butafenacil), carfentrazone, carfentrazone-ethyl, chlomethoxyfen, anthraquinone. Cinidon-ethyl, fluaz〇iate, fluoroquinone. Flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, carboxyfluoride Chloroether (fluor〇glyCOfen), fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, haloprofen (halosafen), lactoflufen (lact0fen), propargyl oxazol (oxadiargyl), oxadiazon 'oxyfluorfen', pentoxazone (pentoxazone), fluoxetine ( Profiuaz〇i), pyraclonil, pyrafiufen, pyraflufen-ethyl, safiufenacil, sulfentrazone, thiadiazole Thidiazimin, 2_chloro-5-[3 6·dihydro-3-methyl-2,6-di-oxy-4-(trifluoromethyl)-1(2 ugly)-pyrimidinyl ]-4-fluoro-N-[(isopropyl)methylamine sulfonyl]benzamide (B); CAS 372137-35-4), [3-[2-Ga-4-fluoro-5 -(1-methyl-6-trifluorodecyl-2,4-di-oxy-1,2,3,4-tetrahydropyrimidine Acetyl-3-yl)phenoxy]·2-α-pyridyloxy]acetate (B_2; CAS 353292-31-6), Ν-ethyl-3-(2,6-diqi-4- Trifluoromethyl phenoxy)-5-methyl-lif-pyrazole-l decylamine (B_3; CAS 452098-92-9), N-tetrahydrofuran oxime ·3·(26_二气_4三Fluoroquinophenoxy)_ 5-methyl-1//-pyrazole-1-carboxamide (B-4; cas 915396-43-9), Ν-ethyl-3-(2-chloro- 6-Fluoro-4-trifluoromethylphenoxy) _5 曱 丨 ugly. Bis-zolylamine (Β·5; CAS 452099-05-7) and N-tetrahydrofuranmethyl-3-(2-chloro-I5H70.doc • 42· 201127285 6-fluoro-4-trifluoromethyl Phenoxy)-5-methyl-1//-pyrazole-1-decylamine (B-6; CAS 452100-03-7); b5) Group of bleach herbicides: benzoxen (aclonifen) ), amitrol, beflubutamid, benzobicyclon, benzofenap, cl〇mazone, diflufenican , fluridone, flurochloridone, flurtamone, isoxanut〇le, mesotrione, norflurazon , fluoxetine (pic〇iinafen), pyrazone (pyrasulfutole), pyrazolynate, pyrazoxyfen, sulc〇tri〇ne, sulphate Ketone (tefuryltrione), tembotrione, topramezone, 4-carbyl-3-[[2-[(2-methoxyethoxy)] thio]-6-(three Fluorinyl)-3-. Bipyridyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one (B-7; CAS 352010-68-5) and 4-(3-trifluoromethylphenyloxy)-2- (4-Trifluoromethylphenyl)pyrimidine (B-8; CAS 180608-33-7); b6) Groups from EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium and glyphosate - triterpene (sulfosate); b7) from the group of branamine synthase inhibitors: bilanaphos (bialaphos), bilapia sodium, guava and solid kill Oxalate; b8) from DHP synthase inhibitors: asulam; 5 151170.doc -43- 201127285 b9) from mitotic inhibitors: amiprophos, guanylamine Amiprophos-methyl, benfluralin, butamiphos, butralin, carbeamide, chlorpropham, chlorthal, Chlorthal-dimethyl, dinitramine, dithiopyr, ethalfluralin, fluchloralin, oryzalin, Pendimethalin Prodiamine, propham, propyzamide, tebutam, thiazopyr and trifluralin; blO) from VLCFA inhibitors Group: acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethanamid ), dimethenamid-P, diphenamid, fentrazamide, flufenacet, mefenacet, metazachlor , metolachlor, metolachlor-S, naproanilide, napropamide, pethoxamid, piperophos, pretilachlor ), propachlor, propisochlor, pyroxasulfone (KIH-485) and thenylchlor; compound of formula 2:

151170.doc 201127285 其中代號具有以下含義： γ為如開始時駭義之笨基或5或巧雜芳基，該等基團可 經1至3個基團Raa取代^、^、…、以為卜齒素或 C1-C4院基；X為〇或NH ; η為〇或1。 式2化合物尤其具有以下含義： Υ為151170.doc 201127285 wherein the code has the following meaning: γ is a stupid base or a 5 or a heteroaryl group as defined at the beginning, and these groups may be substituted by 1 to 3 groups Raa ^, ^, ..., Or C1-C4 hospital base; X is 〇 or NH; η is 〇 or 1. The compound of formula 2 has the following meanings in particular:

Λ 其中#表示與分子骨架鍵結之鍵；且 R R R 、尺24為 H、C1、F 或 CH3 ; R25為鹵素、CVC4 烷基或C丨-c4_烷基；為c丨·c4烷基；r27為齒素、Ci_C4 烷氧基或C「C4鹵烷氧基；R28為Η、鹵素、c!-c4烷基、C!- C4齒院基或Cl_C4_烷氧基；m為〇、1、2或3 ; X為氧；η為 0或1。 較佳式2化合物具有以下含義：# where # represents a bond to the molecular skeleton; and RRR, rule 24 is H, C1, F or CH3; R25 is halogen, CVC4 alkyl or C丨-c4_alkyl; c丨·c4 alkyl; R27 is dentate, Ci_C4 alkoxy or C"C4 haloalkoxy; R28 is hydrazine, halogen, c!-c4 alkyl, C!-C4 dentate or Cl_C4_alkoxy; m is 〇, 1 , 2 or 3; X is oxygen; η is 0 or 1. The compound of the preferred formula 2 has the following meanings:

R2、H r22、R23為 F ; R24 為 Η或 F ; X為氧；η為 0或 1。 尤佳式2化合物為· 3_[5_(2,2-二氟乙氧基）-1-甲基-3-三氟甲基-1Η-吡唑-4-基曱 烷磺醯基]_4氟、5,5-二甲基-4,5-二氫異噁唑（2-1) ; 3-{[5-(2,2-二氟-乙氧基甲基_3_三氟甲基·1Η_0比唑_4•基]氟甲 烧確酿基}_5,5~二甲基-4,5-二氫異噁唑（2-2) ; 4-(4-氟-5,5- J5J170.doc • 45-R2, Hr22, and R23 are F; R24 is Η or F; X is oxygen; η is 0 or 1. The compound of formula 2 is · 3_[5_(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1Η-pyrazole-4-yldecanesulfonyl]_4fluoro ,5,5-Dimethyl-4,5-dihydroisoxazole (2-1); 3-{[5-(2,2-difluoro-ethoxymethyl_3_trifluoromethyl) · 1Η_0 azole _4• yl] fluoromethanthine kiln}_5,5~ dimethyl-4,5-dihydroisoxazole (2-2); 4-(4-fluoro-5,5- J5J170.doc • 45-

I 201127285 一曱基-4,5-二氫異噁唑·3-磺醯基甲基）_2•甲基_5_三氟甲 基·2Η·[1，2,3]二唾（2-3) ; 4-[(5,5-二甲基·4,5·二氫異噁峻 _ 3-碩醯基）氟曱基]-2-曱基_5_三氟曱基_2Η [1，2 3]***（2_ 4)，4-(5,5·二曱基-4,5-二氫異噁唑·3•磺醯基甲基广2甲基· 5-二氣甲基-2Η-[1，2,3]三唾（2_5) ; 3_{[5(22_二氟乙氧基）_ 1-曱基-3-二氟甲基-1Η-吡唑_4•基]二氟甲烷磺醯基卜5 5_二 甲基-4,5·二氫異嗔嗤（2-6) ; 4_[(5,5·二曱基_4,5_二氫異噁 唑-3·磺醯基）二氟甲基]-2-甲基-5•三氟甲基·2Η [12 3]*** (2-7) ’ 3-{[5-(2,2-二氟乙氧基）甲基_3_三氟曱基_1Η•吡 唑-4-基]二氟甲烷磺醯基氟-5,5_二甲基_4,5_二氫異噁 唑（2-8) ; 4-[二氟-(4-氟-5,5-二曱基·4,5_二氫異噁唑_3_磺醯 基）曱基]-2-曱基-5-二氟曱基_21^-[1，2,3]三唾（2-9); bll)來自纖維素生物合成抑制劑之群： 氯硫醯草胺（chlorthiamid)、二氯笨腈（dichlobenil)、氟 胺草唾（flupoxam)及異噁醯草胺（is〇xaben); bl2)來自解偶合除草劑之群： 達諾殺（dinoseb)、特樂酚（dinoterb)及DN〇c與其鹽； bl3)來自植物生長素除草劑之群： 2,4-D及其鹽與醋、2,4-DB及其鹽與酯、氣胺基吡啶酸 (aminopyralid)及其鹽（諸如氣胺基吡啶酸_參（2_羥基丙基） 銨）與其醋、草除靈（benazolin)、乙基草除靈（benazolin-ethyl)、草滅平（chloramben)及其鹽與酯、克普草（clomepr〇p)、 畢克草（clopyralid)及其鹽與酯、麥草畏（dicamba)及其鹽與 酯、2,4-滴丙酸（dichlorprop)及其鹽與酯、精2,4-滴丙酸 151170.doc -46· 201127285 (dichlorprop-P)及其鹽與酯、氟氯比（fluroxypyr)、說氣比-布托美（fluroxypyr-butometyl)、氟氯比-甲基庚SI (fluroxypyr-meptyl)、MCPA及其鹽與醋、硫乙基 MCPA、 MCPB及其鹽與醋、二甲四氯丙酸（mecoprop)及其鹽與 酯、精二曱四氯丙酸（mecoprop-P)及其鹽與酯、毒莠定 (picloram)及其鹽與醋、快克草（quinclorac)、氣曱啥琳酸 (quinmerac)、TBA (2,3,6)及其鹽與醋、三氣比（triclopyr) 及其鹽與酯以及5,6-二氯-2-環丙基·4·嘧啶甲酸（B-9 ; CAS 858956-08-8)及其鹽與酯； b 14)來自植物生長素輸送抑制劑之f 二氟"比隆 (diflufenzopyr)、二氟°比隆鈉鹽（diflufenzopyr-sodium)、萘 草胺（naptalam)及萘草胺納鹽（naptalam-sodium); b 1 5)來自其他除草劑之群：溴丁酿草胺（bromobutide)、 整形醇（chlorflurenol)、曱基整形醇（ehlorflurenol-methyl)、環庚草謎（cinmethylin)、苄草隆（cumyluron)、得 拉本（dalapon)、棉隆（dazomet)、野燕枯（difenzoquat)、曱 基硫酸野燕枯（difenzoquat-metilsulfate)、穫萎得 (dimethipin)、DSMA、汰草龍（dymron)、茵多酸（endothal) 及其鹽、乙氧苯草胺（etobenzanid)、麥草氟（flamprop)、麥 草氟異丙酯（flamprop-isopropyl)、麥草氟曱酯（flamprop-methyl)、高效麥草氟異丙酯（flamprop-M-isopropyl)、高效 麥草氟曱酯（flamprop-M-methyl)、抑草丁（flurenol)、丁基 抑草丁（Hurenol-butyl)、°夫嘲醇（flurprimidol)、殺木膦 (fosamine)、殺木膦敍鹽（fosamine-ammonium)、茚草 _ 151170.doc -47- 201127285 (indanofan)、馬來酿肼（maleic hydrazide)、氟續酿草胺 (mefluidide)、威百故（metam)、疊 ι 甲烧（methyl azide)、 溴曱烷（methyl bromide)、甲基汰草龍（methyl-dymron)、碘 甲烧（methyl iodide)、MSMA、油酸（oleic acid)、。惡嘻草嗣 (oxaziclomefone)、壬酸（peiarg〇nic acid)、稗草丹 (pyributicarb)、滅藻醌（quinociamine)、三嗪氟草胺 (triaziflam)、三地芬（tridiphane)以及 6-氯-3-(2-環丙基-6-甲基苯氧基）-4-違嗪醇（B-10; CAS 499223-49-3)及其鹽與 酯。. 較佳安全劑C之實例為解草酮（benoxacor)、解毒啥 (cloquintocet)、解草胺腈（cyoinetrinil)、噻普磺醯胺 (cyprosulfamide)、二氯丙烯胺（dichlormid)、迪赛隆 (dicyclonone)、迪艾索諾（dietholate)、解草唑 (fenchlorazole)、解草啶（fencl〇rim) ' 解草安（fiurazole)、 肟草安（fluxofenim)、解草噁唑（furilazole)、雙苯噁唑酸 (isoxadifen)、 吡唑解草酯（mefenpyr)、 甲苯諾 (mephenate)、萘二甲酸酐、解草腈（oxabetrinil)、4-(二氯 乙醯基）-1-氧雜-4-氮雜螺[4.5]癸烷（B-ll ; MON4660，CAS 7 1526-07-3)及2,2,5·三曱基-3-(二氯乙醯基）·1，3-噁唑啶 (Β-12 ’· R-29148，CAS 52836-31-4)。 群bl)至bl 5)之活性化合物及安全劑c為已知除草劑及安 全劑’參見例如 The Compendium of Pesticide Common Names(http://www.alanwood.net/pesticides/) ； B. Hock, C. Fedtke，R· R. Schmidt，Herbizide [除草劑]，Georg Thieme 151170.doc -48- 201127285I 201127285 monomethyl-4,5-dihydroisoxazole·3-sulfonylmethyl)_2•methyl_5_trifluoromethyl·2Η·[1,2,3]disc (2- 3); 4-[(5,5-Dimethyl·4,5·dihydroisoxanthene-3-pyringyl)fluoroindolyl]-2-mercapto-5_trifluoroindenyl-2-indole [ 1,2 3]triazole (2_ 4), 4-(5,5·didecyl-4,5-dihydroisoxazole·3•sulfonylmethyl 2 methyl·5- 2 gas Base-2Η-[1,2,3]tris(2_5) ; 3_{[5(22-difluoroethoxy)-1-pyryl-3-difluoromethyl-1Η-pyrazole_4• Difluoromethanesulfonyl bromide 5 5_dimethyl-4,5·dihydroisoindole (2-6) ; 4_[(5,5·diindolyl-4,5-dihydroisoxime) Oxazole-3·sulfonyl)difluoromethyl]-2-methyl-5•trifluoromethyl·2Η [12 3]triazole (2-7) ' 3-{[5-(2,2- Difluoroethoxy)methyl_3_trifluoromethyl-1Η•pyrazol-4-yl]difluoromethanesulfonylfluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-8) ; 4-[Difluoro-(4-fluoro-5,5-dimercapto-4,5-dihydroisoxazole_3_sulfonyl)indolyl]-2-indenyl- 5-difluorodecyl _21^-[1,2,3]trisole (2-9); bll) from the group of cellulose biosynthesis inhibitors: chlorthiamid, dichlorobenzonitrile (dichlobenil) , Flupoxam and is〇xaben; bl2) from de-coupled herbicides: dinoseb, dinoterb and DN〇c and its salts; Bl3) from the group of auxin herbicides: 2,4-D and its salts with vinegar, 2,4-DB and its salts and esters, aminopyralids and their salts (such as amphetamine pyridine) Acid _ ginseng (2-hydroxypropyl) ammonium) with vinegar, benazolin, benazolin-ethyl, chloramben and its salts and esters, clef 〇p), clopyralid and its salts and esters, dicamba and its salts and esters, 2,4-dipropionic acid (dichlorprop) and its salts and esters, fine 2,4-D Acid 151170.doc -46· 201127285 (dichlorprop-P) and its salts and esters, fluroxypyr, fluoxypyr-butometyl, chlorofluoro-methyl-sulphide (fluroxypyr- Meptyl), MCPA and its salts and vinegar, thioethyl MCPA, MCPB and its salts and vinegar, mecoprop and its salts and esters, mecoprop-P and Its salt and ester, chlorpyrifos (piclor Am) and its salts and vinegar, quinclorac, quinmerac, TBA (2,3,6) and its salts and vinegar, triclopyr and its salts and esters 5,6-Dichloro-2-cyclopropyl·4·pyrimidinecarboxylic acid (B-9; CAS 858956-08-8) and its salts and esters; b 14) f-fluorine from auxin transport inhibitors ; diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium; b 1 5) from other herbicides: bromine Bromobutide, chlorflurenol, ehlorflurenol-methyl, cinmethylin, cumyluron, dalapon, damoon ), difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, ethoxybenzene Etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, high-efficiency wheat fluoroisopropyl ester (fla) mprop-M-isopropyl), high-efficiency wheat fluprop-M-methyl, flurenol, Hurenol-butyl, flurprimidol, chlorpyrifos Fosamine), fosamine-ammonium, valerian _ 151170.doc -47- 201127285 (indanofan), maleic hydrazide, mefluidide, weibai Metam), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid. Oxaziclomefone, peiarg〇nic acid, pyributicarb, quinociamine, triaziflam, tridiphane, and 6-chlorine -3-(2-Cyclopropyl-6-methylphenoxy)-4-zinoxazol (B-10; CAS 499223-49-3) and its salts and esters. Examples of preferred safeners C are benoxacor, cloquintocet, cyoinetrinil, cyprosulfamide, dichlormid, and disellon. (dicyclonone), dietholt, fenchlorazole, fencl〇rim 'fiurazole, fluxofenim, furilazole, Isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroethenyl)-1-oxa -4-azaspiro[4.5]decane (B-ll; MON4660, CAS 7 1526-07-3) and 2,2,5·trimethyl-3-(dichloroethenyl)·1,3 - oxazolidine (Β-12 '· R-29148, CAS 52836-31-4). The active compounds and safeners c of groups bl) to bl 5) are known herbicides and safeners 'see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [herbicide], Georg Thieme 151170.doc -48- 201127285

Verlag，Stuttgart, 1995。其他除草活性化合物由WO 96/26202、WO 97/41116、WO 97/41117、WO 97/41118、 WO 01/83459及 WO 2008/074991 及 W. Kilmer 等人（編）， 「Modern Crop Protection Compounds」，第 1 卷，Wiley VCH，2007及其中所引用之文獻已知。 本發明之化合物I及組合物亦可能具有植物強化作用。 因此，其適合於調動植物針對不當微生物（諸如有害真菌 以及病毒及細菌）攻擊之防禦系統。在本發明情形下，植 物強化（誘發抗性）物質應理解為意謂能夠以一定方式刺激 經處理植物之防禦系統使得在隨後接種不當微生物時，經 處理植物對此等微生物顯示相當大程度之抗性的彼等物 質。 化合物I可用於在處理之後特定時段内保護植物免受不 當微生物之攻擊。實現其保護作用之時段通常在用化合物 I處理植物之後延續1天至28天 '較佳1天至14天，或在處 理種子之後在播種之後延續高達9個月。 本發明之化合物I及組合物亦適用於提高收穫產量。 此外，其毒性較小且植物能良好耐受。 【實施方式】 下文以實例方式說明式I化合物的製備。 合成實例 在適當變化起始物質的情況下，使用以下合成實例中所 提供之程序獲得其他化合物I。以此方式獲得之化合物以 及物理數據列於下表中。Verlag, Stuttgart, 1995. Other herbicidal active compounds are described in WO 96/26202, WO 97/41116, WO 97/41117, WO 97/41118, WO 01/83459 and WO 2008/074991 and W. Kilmer et al. (eds.), "Modern Crop Protection Compounds" , Vol. 1, Wiley VCH, 2007 and the literature cited therein are known. The compounds I and compositions of the invention may also have a plant strengthening effect. Therefore, it is suitable for mobilizing plants against defense systems against the attack of inappropriate microorganisms such as harmful fungi as well as viruses and bacteria. In the context of the present invention, a plant-fortified (induced resistance) substance is understood to mean a defense system capable of stimulating a treated plant in a manner such that when subsequently inoculated with an inappropriate microorganism, the treated plant shows a considerable degree to the microorganism. Resistance to their substances. Compound I can be used to protect plants from attack by inappropriate microorganisms for a specific period of time after treatment. The period of time for which protection is effected is usually from 1 day to 28 days after treatment of the plant with Compound I, preferably from 1 day to 14 days, or up to 9 months after seeding after treatment of the seed. The compounds I and compositions of the invention are also suitable for increasing harvest yield. In addition, it is less toxic and the plants are well tolerated. [Examples] The preparation of the compounds of formula I is illustrated below by way of example. Synthesis Example Other compounds I were obtained using the procedure provided in the following synthesis examples, with appropriate changes to the starting materials. The compounds obtained in this way and the physical data are listed in the table below.

S 151170.doc -49- 201127285 如下所示之產物藉由熔點測定、藉*NMR光譜法或藉由 HPLC-MS光譜法測定之質量或滯留時間（RT ;[分 鐘])表徵。 [HPLC-MS=高效液相層析聯合質譜法； HPLC管柱： RP-18 管柱（Chromolith Speed ROD，來自 Merck KgaA，S 151170.doc -49- 201127285 The product shown below is characterized by melting point determination, by *NMR spectroscopy or by mass or residence time (RT; [minutes]) as determined by HPLC-MS spectroscopy. [HPLC-MS = high performance liquid chromatography coupled with mass spectrometry; HPLC column: RP-18 column (Chromolith Speed ROD, from Merck KgaA,

Germany)，50M.6 mm ;移動相：乙腈+〇 1%三氟乙酸 (TFA)/水+0·1ο/〇 TFA，使用經5分鐘5:95至i〇〇:〇之梯度，在 40 C下’流動速率1.8 ml/min。 MS :四極電喷霧電離’ 80V(正離子模式）。] I.製備實例 實例1 :製備3-(5-氣-2-氟苯基）_4-氰基_4_(4_氟苯基）丁 酸三氟甲酯 步驟1 : 3-(5-氣-2-氟苯基）-4-氰基-4-(4-氟苯基）丁酸甲 酯（參考 EP-A 266 725) 在-78C下’將4-氟本基乙腈於250 ml四氫。夫喊（THF)中 之溶液逐滴添加至54.89 g第三丁醇鉀於250 ml THF中之溶 液中。10分鐘後，緩慢添加100.00 g 3_(5_氯_2_氟苯基）丙 婦酸甲醋於300 ml THF中之溶液。在_78乞下歷經3〇分鐘 後，藉由添加氣化銨溶液終止反應。用乙酸乙酯萃取混合 物。將2 ml二氮（1，3)雙環[5.4.0]十一烷（DBU)添加至有機 相中’且攪拌混合物1小時。添加丨〇%濃度之HCi後，乾燥 有機相且減壓移除溶劑《得到丨63 g標題化合物（蘇型/赤型 比率 1.2:1)。 15J170.doc -50· 201127285 步驟2 : 3-(5-氯_2_氟苯基）_4_氰基·4·(4_氟苯基）丁酸 將12.17 g氫氧化链於3〇〇 ml水中之溶液添加至161 6〇旦 曱西曰於300 ml THF中之溶液中，且在2〇-25。(：下攪拌混合 物。添加10%濃度之HC1後，用乙酸乙酯萃取混合物。乾 燥經合併之有機相且減壓移除溶劑。得到丨55 g標題化合 物（蘇型/赤型比率1:2)。 步驟3 : 3-(5-氯-2-氟苯基）-4-氰基-4-(4-氟苯基）丁酸三 氟曱酯 在 2.5 ml CH2C12 中攪拌 66.0 mg 羧酸、40.2 mg (2-(7-氮 雜-1H-笨并三。坐-丨-基四甲錁六氟磷酸鹽及56 5 mg 1-乙基-3-(3-二曱基胺基丙基）碳化二亞胺達約15小時。 添加2N HC1後’用飽和碳酸氫銨溶液及氯化鈉溶液洗滌混 合物。乾燥有機相。減壓移除溶劑後，在石夕膠上（環己烧： 乙酸乙醋9:1-4:1)純化粗產物。接著添加2 mi CH2C12及2 ml DBU，且在20-25。(：下攪拌混合物2小時。用2N HC1、 飽和碳酸氫銨溶液及氣化鈉溶液洗滌有機相並乾燥。移除 溶劑，得到25 mg標題化合物（HPLC-MS: 3.761 min.)。 實例2 :製備3-(2-氣-5-氟苯基）-4-氰基-4-(4-氟笨基）丁 酸2,2-二氟乙酯 步驟1 : 3-(2-氣-5-氟苯基）-4-氰基·4·(4-氟苯基）丁酸甲酯 在-78°C下’將1.89 g 4-氟苯基乙腈於5 ml THF中之溶液 逐滴添加至1.65 g第三丁醇鉀於1〇〇 ml THF中之溶液中， 且在-78°C下攪拌混合物10分鐘。接著緩慢添加3-(2-氯-5-氟苯基）丙烯酸甲酯於l〇ml THF中之溶液。在-78°C下歷經 151170.doc 201127285 30分鐘後’藉由添加飽和氣化錄溶液終止反應^用乙酸乙 S旨萃取’乾燥有機相’過遽且減壓移除溶劑之後，使用乙 酸乙醋：環己燒1:10在石夕膠上純化殘餘物。得到4.9 g標題化 合物。 乂驟2 3 (2-氣·5·氟笨基）_4_氰基_4_(‘氟苯基）丁酸 將〇.37 g氫氧化鋰於5〇 ml水中之溶液添加至49 §步驟1 之甲S曰於50 mi THF中之溶液中，且在2〇_25°C下授拌混合 物为15】時。另外添加0· 1 g氫氧化經後，在2〇_25°C下再 次攪拌反應混合物3小時。減壓移除有機溶劑後，將水添 加至殘餘物中且用2N HC1酸化混合物。用乙酸乙酯萃取， 乾燥有機相，過濾，減壓移除溶劑且使用甲醇/水進行RP 層析’得到3.0 g標題化合物。 步驟3 : 3-(2-氯-5-氟苯基）·4-氰基-4-(4-氟苯基）丁酸2,2_ 一氣乙酉旨 將0.12 g 3·羥基***幷[4,5-b]吡啶及0.17 g 1-乙基·3_(3_ 一甲基胺基丙基）碳化二亞胺鹽酸鹽添加至0.2 g步驟2之叛 酸於10 ml二氯甲烷中之溶液中。攪拌反應混合物1〇分 鐘接著添加〇 〇6 g 2,2-二氟乙醇，且在2〇-25°C下攪拌混 合物約15小時。用飽和氯化銨溶液及碳酸氫鈉溶液洗滌 後’減壓移除溶劑且藉由使用乙酸乙酯：環己烷1:1〇之矽膠 s柱層析純化殘餘物。得到86 mg標題化合物（赤型/蘇型 1:2) 〇 表1 :式I化合物：Germany), 50M.6 mm; mobile phase: acetonitrile + hydrazine 1% trifluoroacetic acid (TFA) / water + 0 · 1 ο / 〇 TFA, using 5:95 to i 〇〇: gradient of 〇 for 5 minutes, at 40 Under C, the flow rate was 1.8 ml/min. MS: Tetrapolar electrospray ionization '80V (positive ion mode). I. Preparation Example Example 1: Preparation of 3-(5-Gas-2-fluorophenyl)- 4-cyano-4-4-(4-fluorophenyl)butanoic acid trifluoromethyl ester Step 1: 3-(5-gas Methyl 2-fluorophenyl)-4-cyano-4-(4-fluorophenyl)butanoate (Ref. EP-A 266 725) '- 4-Fenyl acetonitrile in 250 ml at -78C hydrogen. The solution in THF was added dropwise to a solution of 54.89 g of potassium t-butoxide in 250 ml of THF. After 10 minutes, a solution of 100.00 g of 3_(5-chloro-2-fluorophenyl)glycolic acid in THF was added slowly in 300 ml of THF. After 3 minutes at -78 Torr, the reaction was terminated by the addition of a vaporized ammonium solution. The mixture was extracted with ethyl acetate. 2 ml of dinitro(1,3)bicyclo[5.4.0]undecane (DBU) was added to the organic phase and the mixture was stirred for 1 hour. After the addition of 丨〇% concentration of HCi, the organic phase was dried and the solvent was removed under reduced pressure to give <RTI ID=0.0>> 15J170.doc -50· 201127285 Step 2: 3-(5-Chloro-2-fluorophenyl)_4_cyano·4·(4-fluorophenyl)butyric acid 12.17 g of hydroxide chain in 3〇〇ml The solution in water was added to a solution of 16 6 〇 曱 曱 300 in 300 ml of THF, and at 2 〇-25. (The mixture was stirred under stirring. After adding 10% strength of HCl, the mixture was extracted with ethyl acetate. The combined organic phases were dried and solvent was evaporated under reduced pressure to give the title compound: s. Step 3: 3-(5-chloro-2-fluorophenyl)-4-cyano-4-(4-fluorophenyl)butyric acid trifluorodecyl ester was stirred in 2.5 ml of CH2C12 with 66.0 mg of carboxylic acid. 40.2 mg (2-(7-aza-1H-benzotrim. sit-indole-yltetramethylphosphonium hexafluorophosphate and 56 5 mg 1-ethyl-3-(3-didecylaminopropyl) Carbide diimine for about 15 hours. After adding 2N HC1, the mixture was washed with saturated ammonium bicarbonate solution and sodium chloride solution. The organic phase was dried. After removing the solvent under reduced pressure, it was on the stone gel (cyclohexane): The crude product was purified by acetic acid ethyl acetate 9:1-4:1). Then 2 mi of CH2C12 and 2 ml of DBU were added, and the mixture was stirred at 20-25 for 2 hours. 2N HCl, saturated ammonium bicarbonate solution and gas The organic phase was washed with a sodium chloride solution and dried. The solvent was evaporated to give 25 mg of the title compound (HPLC-MS: 3.761 min.). Example 2: Preparation of 3-(2-a-5-fluorophenyl)-4-cyano -4-(4-fluorophenyl)butyric acid 2,2-difluoroethyl ester step 1 : 3-(2-A-5-fluorophenyl)-4-cyano-4(4-fluorophenyl)butanoic acid methyl ester at -78 ° C '1.89 g of 4-fluorophenylacetonitrile A solution of 5 ml of THF was added dropwise to a solution of 1.65 g of potassium t-butoxide in 1 mL of THF, and the mixture was stirred at -78 ° C for 10 minutes, followed by the slow addition of 3-(2-chloro- A solution of methyl 5-fluorophenyl)acrylate in 1 〇ml of THF. After 30 minutes at -78 °C after 151170.doc 201127285, the reaction was terminated by the addition of a saturated gasification recording solution. After the 'dry organic phase' was passed over and the solvent was removed under reduced pressure, the residue was purified using ethyl acetate: hexanes: 1:10 to afford 4.9 g of the title compound. 5·Fluoroyl)_4_Cyano_4_('Fluorophenyl)butyric acid Add a solution of 3737 g of lithium hydroxide in 5 〇ml of water to 49 § Step 1 in a 50 THF In the solution, and the mixing mixture was 15 at 2 〇 25 ° C. After adding 0.1 g of hydrogen hydroxide, the reaction mixture was stirred again at 2 〇 25 ° C for 3 hours. After addition of the organic solvent, water was added to the residue and 2N HCl acid was used. The mixture was extracted with EtOAc, EtOAc (EtOAc m. Base) · 4-cyano-4-(4-fluorophenyl)butyric acid 2,2_ one gas ethyl hydrazine 0.12 g 3 · hydroxytriazolium [4,5-b] pyridine and 0.17 g 1-ethyl· 3-(3-Methylaminopropyl)carbodiimide hydrochloride was added to a solution of 0.2 g of the tarenic acid in Step 2 in 10 ml of dichloromethane. The reaction mixture was stirred for 1 Torr, then 〇 6 g of 2,2-difluoroethanol was added, and the mixture was stirred at 2 to 25 ° C for about 15 hours. After washing with a saturated ammonium chloride solution and a sodium hydrogen carbonate solution, the solvent was removed under reduced pressure and the residue was purified by EtOAc EtOAc EtOAc Obtained 86 mg of the title compound (erythro/threo 1:2) 〇 Table 1: Compound of formula I:

S 151170.doc •52· 201127285S 151170.doc •52· 201127285

編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-1 4-F ch2c=ch F F 3.485/380 [M+Naf 1-2 3,4-Cl2 ch3 F F 3.886/352 [M-31]+ 1-3 3-C1 ch3 F F 3.530/367 [M+18]+ 1-4 3,5-Cl2 ch3 F F 3.926/384 [M+H]+ 1-5 4-C1 ch3 F F 3.674/350 [M+H]+ 1-6 4-C1 ch2och F F 3.752/374 [M+H]+ 1-7 3-F,4-Cl H F F 3.152/375 [M+Na]+ 1-8 4-C1 H F F 3.103/358 [M+Na]+ 1-9 4-F H F F 3.043/342 [M+Na]+ 1-10 3-F,4-Cl CH2CHF2 F F 3.626/440 [M+Na]+ 1-11 4-C1 CH2CHF2 F F 3.594/422 [M+Na]+ 1-12 4-F CH2CHF2 F F 3.429/405 [M+Na]+ 1-13 3-F,4-Cl ch2cf3 F F 4.009/336 [M-99]+ 1-14 4-C1 CH2CF3 F F 4.043/440 [M+Na]+ 1-15 4-F ch2cf3 F F 3.838/424 [M+Na]+ 1-16 3-F,4-Cl ch2c=ch F F 3.580/414 [M+Na]+ 1-17 3,4-F2 ch2chf2 Br F 3.855/484 [M+Na]+ 1-18 4-F ch3 Br F 3.800/396 [M+H]+ 1-19 3,4-F2 CH20CH3 Br F 3.577/484 [M+Na]+ 1-20 4-F H Br F 3.035/404 [M+Na]+ 1-21 4-C1 ch3 Br F 3.636/434 [M+Na]+ 1-22 3,4_F2 ch3 Br F 3.511/436 [M+Na]+ 1-23 4-F CH20CH3 Br F 3.475/448 [M+Na]+ 1-24 4-C1 CH20CH3 Br F 3.696/464 [M+Na]+ 1-25 4-C1 CH2CHF2 Br F 3.981/484 [M+Na]+ 1-26 4-F ch3 Cl F 3.494/372 [M+Na]+ 1-27 4-F ch2och Cl F 3.534/396 [M+Na]+No. R„ R1 R2 R3 Physical data (HPLC: RT[min]/m/z) 1-1 4-F ch2c=ch FF 3.485/380 [M+Naf 1-2 3,4-Cl2 ch3 FF 3.886/352 [M-31]+ 1-3 3-C1 ch3 FF 3.530/367 [M+18]+ 1-4 3,5-Cl2 ch3 FF 3.926/384 [M+H]+ 1-5 4-C1 ch3 FF 3.674/350 [M+H]+ 1-6 4-C1 ch2och FF 3.752/374 [M+H]+ 1-7 3-F,4-Cl HFF 3.152/375 [M+Na]+ 1-8 4 -C1 HFF 3.103/358 [M+Na]+ 1-9 4-FHFF 3.043/342 [M+Na]+ 1-10 3-F,4-Cl CH2CHF2 FF 3.626/440 [M+Na]+ 1- 11 4-C1 CH2CHF2 FF 3.594/422 [M+Na]+ 1-12 4-F CH2CHF2 FF 3.429/405 [M+Na]+ 1-13 3-F,4-Cl ch2cf3 FF 4.009/336 [M- 99]+ 1-14 4-C1 CH2CF3 FF 4.043/440 [M+Na]+ 1-15 4-F ch2cf3 FF 3.838/424 [M+Na]+ 1-16 3-F,4-Cl ch2c=ch FF 3.580/414 [M+Na]+ 1-17 3,4-F2 ch2chf2 Br F 3.855/484 [M+Na]+ 1-18 4-F ch3 Br F 3.800/396 [M+H]+ 1- 19 3,4-F2 CH20CH3 Br F 3.577/484 [M+Na]+ 1-20 4-FH Br F 3.035/404 [M+Na]+ 1-21 4-C1 ch3 Br F 3.636/434 [M+ Na]+ 1-22 3,4_F2 ch3 Br F 3.511/436 [M+Na]+ 1-23 4-F CH20CH3 Br F 3.475/448 [M+Na]+ 1-24 4-C1 CH20CH3 Br F 3.696/ 464 [M+Na]+ 1- 25 4-C1 CH2CHF2 Br F 3.981/484 [M+Na]+ 1-26 4-F ch3 Cl F 3.494/372 [M+Na]+ 1-27 4-F ch2och Cl F 3.534/396 [M+Na ]+

S 151170.doc -53- 201127285 編號 Rn R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-28 4-F ch3 Cl cf3 4.088/399 [M+Na]+ 1-29 3-CN ch3 Cl F 3.309/379 [M+Na]+ 1-30 3-F，4-Cl ch3 Cl F 3.941/384 [M+H]+ 1-31 4-F ch2och3 Cl F 3.523/397 [M+H]+ 1-32 4-F CH2N(CH3)COOH Cl F 3.642/459 [M+Na]+ 1-33 4-F CH2CHF2 Cl F 3.798/400 M+H]+ 1-34 3-F ch3 Cl F 1-35 - ch3 Cl F 3.578/332 [M+H]+ 1-36 '4-F ch3 Cl nh2 2.735/347 [M+H]+ 1-37 4-F CH2CHF2 Cl Cl 3.881/334 [M-82]+ 1-38 3-CN CH2CHF2 Cl Cl 3.633/341 [M-82]+ 1-39 4-F CH2CF3 Cl F 3.711/440 [M+Na]+ 1-40 3,4-F2 ch3 Cl F 3.695/390 [M+Na]+ 1-41 3,5-F2 ch3 Cl F 3.704/390 [M+Na]+ 1-42 3,4,5-F3 ch3 Cl F 3.655/386 [M+H]+ 1-43 3,4-F2 H Cl F 3.142/378 [M+Na]+ 1-44 3,5-F2 H Cl F 3.143/378 [M+Na]+ 1-45 3,4,5-F3 H Cl F 3.252/394 [M+Na]+ 1-46 3,5-F2 ch3 Cl Cl 3.629/406 [M+Na]+ 1-47 3,4-F2 ch3 Cl Cl 3.621/384 [M+H]+ 1-48 3,4,5-F3 ch3 Cl Cl 3.926/402 [M+H]+ 1-49 3-F ch3 Cl Cl 3.774/368 [M+H]+ 1-50 3-CN ch3 Cl Cl 3.539/373 [M+H]+ 1-51 3,5-F2 H Cl Cl 3.327/370 [M+H]+ 1-52 3,4-F2 H Cl Cl 3.327/372 [M+H]+ 1-53 4-F ch3 Cl Cl 3.559/366 [M+H]+ 1-54 - ch3 Cl Cl 3.691/348 [M+H]+ 1-55 4-C1 ch3 Cl Cl 3.887/384 [M+H]+ 1-56 3,4,5-F3 H Cl Cl 3.432/388 [M+H]+ 1-57 3-F H Cl Cl 3.525/352 [M+H]+ 1-58 3-CN H Cl Cl 2.916/359 [M+H]+ 1-59 4-F H Cl Cl 3.309/352 [M+H]+ 1-60 - H Cl Cl 3.275/334 [M+H]+ 151170.doc •54- 201127285 編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-61 4-C1 H Cl Cl 3.501/368 [M+H]+ 1-62 4-F CH2OCH F Cl 3.779/318 [M-55]+ 1-63 4-F H F Cl 3.226/318 [M-17]+ 1-64 3,5-F2 H F Cl 3.196/336 [M-17]+ 1-65 3-CN H F Cl 2.891/325 [M-17]+ 1-66 3,4-Cl2 ch3 F Cl 4.024/368 [M-31]+ 1-67 - H F Cl 3.154/300 [M-17]+ 1-68 3-F,4-Cl H F Cl 3.464/352 [M-17]+ 1-69 3,4-F2 H F Cl 3.307/336 [M-17]+ 1-70 4-F CH2CHF2 F Cl 3.769/422 [M+Na]+ 1-71 4-F 2-F-C6H4 F Cl 3.957/466 [M+Na]+ 1-72 4-F 2,6-F2-C6H3 F Cl 3.939/463 [M+Na]+ 1-73 4-F 3-F-C6H4 F Cl 3.81/396 [M+Na]+ 1-74 3-Cl,5-F ch2och F Cl 3.916/424 [M+18]+ 1-75 3,4-F2 ch2och F Cl 3.716/392 [M+H]+ 1-76 3-Cl,4-F ch2c=ch F Cl 3.884/425 [M+Na]+ 1-77 3-Cl，5-F CH2CHF2 F Cl 3.933/352 [M-82]+ 1-78 3,4-F2 CH2CHF2 F Cl 3.796/336 [M-81]+ 1-79 3-Cl,4-F CH2CHF2 F Cl 3.911/352 [M-82]+ 1-80 3-Cl,5-F CH2CHF2 F Cl 3.935/352 [M-82]+ 1-81 4-F 2,4-F2-C6H3 F Cl 3.966/484 [M+Na]+ 1-82 3,5-F2 ch2c^ch F Cl 3.788/392 [M+H]+ 1-83 4-C1 CH2CHF2 F Cl 3.947/334 [M-82]+ 1-84 4-C1 H F Cl 3.373/334 [M-18]+ 1-85 3-F,4-Cl CH2C 三 CH F Cl 3.933/408 [M-H]+ 1-86 3,5-F2 CH2CHF2 F Cl 3.804/336 [M-81]+ 1-87 3-F,4-Cl CH2CHF2 F Cl 3.944/352 [M-82]+ 1-88 - CH2CHF2 F Cl 3.719/300 [M-82]+ 1-89 - CH2C=CH F Cl 3.514/300 [M-56]+ 1-90 4-F CH2CF3 F Cl 3.761/320 [M-98]+ 1-91 4-F CH2CH3 F Cl 3.643/364 [M+H]+ 1-92 4-F CH(CH3)2 F Cl 3.792/318 [M-59]+ 151170.doc -55- 201127285 編號 Rn R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-93 4-F F Cl 3.563/420 [M+H]+ 1-94 4-F ch2ch=ch2 F Cl 3.705/376 [M+H]+ 1-95 4-F ch2cn F Cl 3.383/392 [M+18]+ 1-96 4-F H F Cl 3.155/336 [M+H]+ 1-9? 4-F 2^5^2-06¾ F Cl 4.072/462 [M+H]+ 1-98 3-Cl,4-F H F Cl 3.262/352 [M-18]+ 1-99 3,4-Cl2 H F Cl 3.425/409 [M+Na]+ I-100 4-F CH2OCH3 F Cl 3.609/380 [M+H]+ 1-101 3-F H F Cl 3.191/336 [M+H]+ 1-102 3-F CH2C=CH F Cl 3.664/396 [M+Na]+ 1-103 - CH2OCH3 F Cl 3.563/362 [M+H]+ 1-104 3-Cl,4-F CH2OCH3 F Cl 3.791/412 [M-2]+ 1-105 3-CN 2,5-F2-C6H3 F Cl 3.712/468 [M+H]+ 1-106 3-CN CH2OCH3 F Cl 3.229/387 [M+H]+ 1-107 3-CN CH2CHF2 F Cl 3.337/325 [M-81]+ 1-108 3-CN ch2och F Cl 3.320/398 [M+18]+ 1-109 4-C1 ch2och F Cl 3.875/407 [M+17]+ 1-110 4-C1 CH20CH3 F Cl 3.831/413 [M+17]+ 1-111 3-Cl，5-F H F Cl 3.423/352 [M-18]+ 1-112 3,4-Cl2 ch2c=ch F Cl 4.024/423 [M+H]+ 1-113 3,4-Cl2 CH2CHF2 F Cl 4.063/367 [M-83]+ 1-114 3,4-F2 2,5-F2-C6H3 F Cl 3.937/501 [M+Na]+ 1-115 - ch3 F Cl 3.402/353 [M+Na]+ 1-116 3-CN ch3 F Cl 3.473/325 [M-31]+ 1-117 3-F CH2CHF2 F Cl 3.542/422 [M+Na]+ 1-118 3-F CH2CF3 F Cl 3.948/440 [M+Na]+ 1-119 4-F CH2CC13 F Cl 3.973/317 [M-150]+ 1-120 4-F CH2CH2CF3 F Cl 3.735/317 [M-117]+ 1-121 3,4-F2 CH2CF3 F Cl 4.041/336 [M-99]+ 1-122 3-Cl,4-F CH2CF3 F Cl 4.122/352 [M-100]+ 1-123 3,5-F2 CH2CF3 F Cl 3.996/336 [M-99]+ 1-124 3-Cl，5-F CH2CF3 F Cl 4.121/352 [M-100]+ 151170.doc -56- 201127285 編號 Rn R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-125 3-F CH2OCH3 F Cl 3.432/401 [M+Na]+ 1-126 3-N〇2 ch3 F Cl 3.493/399 [M+Na]+ 1-127 3-1 ch3 F Cl 3.870/477 [M+H]+ 1-128 4-1 ch3 F Cl 3.751/458 [M+H]+ 1-129 3-1 H F Cl 3.290/466 [M+Na]+ 1-130 4-1 H F Cl 3.347/466 [M+Na]+ 1-131 3-NH2 ch3 F Cl 2.479/347 [M+H]+ 1-132 3-NHCHO ch3 F Cl 2.883/376 [M+H]+ 1-133 4-F ch2ch=ch-cooch3 F Cl 3.504/434 [M+H]+ 1-134 4-F (£)CH2CH=CH-C^CH F Cl 3.641/422 [M+39]+ 1-135 4-F (Z)CH2CH=CC1CH3 F Cl 3.863/424 [M+Hf 1-136 4-F ch2ch=c(ch3)2 F Cl 3.892/426 [M+Na]+ 1-137 4-F ch2ch=cci2 F Cl 3.466/445 [M+Na]+ 1-138 4-F ⑹ ch2ch=chcf3 F Cl 3.373/466 [M+Na]+ 1-139 4-F (Z)CH2CH=CHCH3 F Cl 3.874/412 [M+Na]+ 1-140 4-F CH2CH2F F Cl 3.482/404 [M+Na]+ 1-141 3,5-F2 CH2CH2F F Cl 3.545/422 [M+Na]+ 1-142 4-F 〇E)CH2CH=CHCH3 F Cl 3.848/412 [M+Na]+ 1-143 4-F ch3 F cf3 3.766/406 [M+Na]+ 1-144 4-F ch2c=ch F cf3 3.71/430 [M+Na]+ 1-145 4-F ch3 F CN 1-146 4-F ch2och F CN 3.627/365 [M+H]+ 1-147 4-F ch3 F N〇2 3.317/383 [M+Na]+ 1-148 4-F ch3 F ocf3 3.656/432 [M+Na]+ 1-149 4-F H F cf3 3.363/392 [M+Na]+ 1-150 4-F ch3 F ch3 3.839/330 [M+H]+ 1-151 3-F,4-Cl ch3 F CN 3.931/384 [M+9]+ 1-152 3-F,4-Cl ch3 F N〇2 3.699/417 [M+Na]+ 1-153 4-C1 ch3 F CN 3.541/357 [M+H]+ 1-154 4-F ch3 F chf2 3.608/343 [M-23]+ 1-155 4-F H F CN 2.813/326 [M+H]+ 1-156 4-F H F N〇2 2.937/363 [M+18]+ 1-157 4-F ch3 F I 3.622/459 [M+18]+ g 151170.doc -57- 201127285 編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-158 3,4-F2 ch3 F I 3.676/477 [M+18]+ 1-159 3,4,5-F3 ch3 F I 3.777/477 [M+18]+ 1-160 3-CN ch3 F I 3.557/438 [M-10]+ 1-161 3-CN ch3 F Br 3.333/420 [M+19]+ 1-162 4-C1 ch3 F N02 3.649/399 [M+Na]+ 1-163 4-Cl，3,5-F2 ch3 F N〇2 3.619/437 [M+Na]+ 1-164 4-Cl,3,5-F2 ch3 F CN 3.724/394 [M+Na]+ 1-165 4-F ch3 F 2-F- C6H4 3.809/409 [M]+ 1-166 4-F ch3 F 3- cf3- C6H4 4.046/359 [M]+ 1-167 4-F ch3 F 3,4,5- f3- c6h2 3.988/445 [M]+ 1-168 4-F ch3 F 4-F- C6H4 3.838/409 [M]+ 1-169 4-F ch3 F c6h5 3.822/391 [M]+ 1-170 4-F ch3 F 3-F- C6H4 3.849/409 [M]+ 1-171 4-F H F Br 3.214/362 [M-18]+ 1-172 4-F CH2CHF2 F Br 3.805/452 [M+8]+ 1-173 4-F ch2cf3 F Br 3.943/452 [M-10]+ 1-174 4-F ch2c=ch F Br 3.741/364 [M-54]+ 1-175 4-C1 ch3 F Br 3.842/412 [M+2]+ 1-176 3-F H F Br 3.198/382 [M+2]+ 1-177 3-CN H F Br 2.920/387 [M]+ 1-178 3,4-F2 H F Br 3.290/398 [M]+ 1-179 3,4,5-F3 H F Br 3.346/416 [M]+ 1-180 3,5-F2 H F Br 3.246/382 [M-16]+ 1-181 4-C1 H F Br 3.406/398 [M+2]+ 1-182 4-F H F chf2 2.794/374 [M+Na]+ 1-183 4-F CH2CF3 F chf2 3.257/456 [M+Na]+ 1-184 4-F CH2OCH3 F chf2 3.450/396 [M+H]+ 1-185 4-F ch3 cf3 Cl 4.005/422 [M+H]+ 151170.doc •58- 201127285S 151170.doc -53- 201127285 No. Rn R1 R2 R3 Physical Data (HPLC: RT[min]/m/z) 1-28 4-F ch3 Cl cf3 4.088/399 [M+Na]+ 1-29 3- CN ch3 Cl F 3.309/379 [M+Na]+ 1-30 3-F,4-Cl ch3 Cl F 3.941/384 [M+H]+ 1-31 4-F ch2och3 Cl F 3.523/397 [M+ H]+ 1-32 4-F CH2N(CH3)COOH Cl F 3.642/459 [M+Na]+ 1-33 4-F CH2CHF2 Cl F 3.798/400 M+H]+ 1-34 3-F ch3 Cl F 1-35 - ch3 Cl F 3.578/332 [M+H]+ 1-36 '4-F ch3 Cl nh2 2.735/347 [M+H]+ 1-37 4-F CH2CHF2 Cl Cl 3.881/334 [M -82]+ 1-38 3-CN CH2CHF2 Cl Cl 3.633/341 [M-82]+ 1-39 4-F CH2CF3 Cl F 3.711/440 [M+Na]+ 1-40 3,4-F2 ch3 Cl F 3.695/390 [M+Na]+ 1-41 3,5-F2 ch3 Cl F 3.704/390 [M+Na]+ 1-42 3,4,5-F3 ch3 Cl F 3.655/386 [M+H ]+ 1-43 3,4-F2 H Cl F 3.142/378 [M+Na]+ 1-44 3,5-F2 H Cl F 3.143/378 [M+Na]+ 1-45 3,4,5 -F3 H Cl F 3.252/394 [M+Na]+ 1-46 3,5-F2 ch3 Cl Cl 3.629/406 [M+Na]+ 1-47 3,4-F2 ch3 Cl Cl 3.621/384 [M +H]+ 1-48 3,4,5-F3 ch3 Cl Cl 3.926/402 [M+H]+ 1-49 3-F ch3 Cl Cl 3.774/368 [M+H]+ 1-50 3-CN Ch3 Cl Cl 3.539/373 [M+H]+ 1-51 3,5-F2 H Cl Cl 3.327/370 [M+H]+ 1-52 3,4-F2 H Cl Cl 3.327/372 [M+H]+ 1-53 4-F ch3 Cl Cl 3.559/366 [M+H]+ 1-54 - ch3 Cl Cl 3.691/348 [M+H]+ 1-55 4-C1 ch3 Cl Cl 3.887/384 [M+H]+ 1-56 3,4,5-F3 H Cl Cl 3.432/388 [M+ H]+ 1-57 3-FH Cl Cl 3.525/352 [M+H]+ 1-58 3-CN H Cl Cl 2.916/359 [M+H]+ 1-59 4-FH Cl Cl 3.309/352 [ M+H]+ 1-60 - H Cl Cl 3.275/334 [M+H]+ 151170.doc •54- 201127285 No. R„ R1 R2 R3 Physical Data (HPLC: RT[min]/m/z) 1- 61 4-C1 H Cl Cl 3.501/368 [M+H]+ 1-62 4-F CH2OCH F Cl 3.779/318 [M-55]+ 1-63 4-FHF Cl 3.226/318 [M-17]+ 1-64 3,5-F2 HF Cl 3.196/336 [M-17]+ 1-65 3-CN HF Cl 2.891/325 [M-17]+ 1-66 3,4-Cl2 ch3 F Cl 4.024/368 [M-31]+ 1-67 - HF Cl 3.154/300 [M-17]+ 1-68 3-F,4-Cl HF Cl 3.464/352 [M-17]+ 1-69 3,4-F2 HF Cl 3.307/336 [M-17]+ 1-70 4-F CH2CHF2 F Cl 3.769/422 [M+Na]+ 1-71 4-F 2-F-C6H4 F Cl 3.957/466 [M+Na] + 1-72 4-F 2,6-F2-C6H3 F Cl 3.939/463 [M+Na]+ 1-73 4-F 3-F-C6H4 F Cl 3.81/396 [M+Na]+ 1-74 3-Cl,5-F ch2och F Cl 3.916/424 [M+18]+ 1-75 3,4-F2 ch2och F Cl 3.716/392 [M+H]+ 1-76 3-Cl,4-F ch2c=ch F Cl 3.884/425 [M+Na]+ 1-77 3-Cl,5-F CH2CHF2 F Cl 3.933/352 [M-82]+ 1-78 3,4-F2 CH2CHF2 F Cl 3.796/336 [M-81]+ 1-79 3-Cl,4-F CH2CHF2 F Cl 3.911/352 [M-82]+ 1- 80 3-Cl,5-F CH2CHF2 F Cl 3.935/352 [M-82]+ 1-81 4-F 2,4-F2-C6H3 F Cl 3.966/484 [M+Na]+ 1-82 3,5 -F2 ch2c^ch F Cl 3.788/392 [M+H]+ 1-83 4-C1 CH2CHF2 F Cl 3.947/334 [M-82]+ 1-84 4-C1 HF Cl 3.373/334 [M-18] + 1-85 3-F,4-Cl CH2C Tri CH F Cl 3.933/408 [MH]+ 1-86 3,5-F2 CH2CHF2 F Cl 3.804/336 [M-81]+ 1-87 3-F, 4-Cl CH2CHF2 F Cl 3.944/352 [M-82]+ 1-88 - CH2CHF2 F Cl 3.719/300 [M-82]+ 1-89 - CH2C=CH F Cl 3.514/300 [M-56]+ 1 -90 4-F CH2CF3 F Cl 3.761/320 [M-98]+ 1-91 4-F CH2CH3 F Cl 3.643/364 [M+H]+ 1-92 4-F CH(CH3)2 F Cl 3.792/ 318 [M-59]+ 151170.doc -55- 201127285 No. Rn R1 R2 R3 Physical Data (HPLC: RT[min]/m/z) 1-93 4-FF Cl 3.563/420 [M+H]+ 1 -94 4-F ch2ch=ch2 F Cl 3.705/376 [M+H]+ 1-95 4-F ch2cn F Cl 3.383/392 [M+18]+ 1-96 4-FHF Cl 3.155/336 [M+ H]+ 1-9? 4-F 2^5^2-06 F Cl 4.072/462 [M+H]+ 1-98 3-Cl,4-FHF Cl 3.262/352 [M-18]+ 1-99 3,4-Cl2 HF Cl 3.425/409 [M+Na]+ I-100 4-F CH2OCH3 F Cl 3.609/380 [M+H]+ 1-101 3-FHF Cl 3.191/336 [M+H]+ 1-102 3-F CH2C=CH F Cl 3.664/396 [M +Na]+ 1-103 - CH2OCH3 F Cl 3.563/362 [M+H]+ 1-104 3-Cl,4-F CH2OCH3 F Cl 3.791/412 [M-2]+ 1-105 3-CN 2, 5-F2-C6H3 F Cl 3.712/468 [M+H]+ 1-106 3-CN CH2OCH3 F Cl 3.229/387 [M+H]+ 1-107 3-CN CH2CHF2 F Cl 3.337/325 [M-81 ]] 1-108 3-CN ch2och F Cl 3.320/398 [M+18]+ 1-109 4-C1 ch2och F Cl 3.875/407 [M+17]+ 1-110 4-C1 CH20CH3 F Cl 3.831/413 [M+17]+ 1-111 3-Cl,5-FHF Cl 3.423/352 [M-18]+ 1-112 3,4-Cl2 ch2c=ch F Cl 4.024/423 [M+H]+ 1- 113 3,4-Cl2 CH2CHF2 F Cl 4.063/367 [M-83]+ 1-114 3,4-F2 2,5-F2-C6H3 F Cl 3.937/501 [M+Na]+ 1-115 - ch3 F Cl 3.402/353 [M+Na]+ 1-116 3-CN ch3 F Cl 3.473/325 [M-31]+ 1-117 3-F CH2CHF2 F Cl 3.542/422 [M+Na]+ 1-118 3 -F CH2CF3 F Cl 3.948/440 [M+Na]+ 1-119 4-F CH2CC13 F Cl 3.973/317 [M-150]+ 1-120 4-F CH2CH2CF3 F Cl 3.735/317 [M-117]+ 1-121 3,4-F2 CH2CF3 F Cl 4.041/336 [M-99]+ 1-122 3-Cl,4-F CH2CF3 F Cl 4.122/352 [M-100]+ 1-123 3,5-F2 CH2CF3 F Cl 3.996/336 [M-99]+ 1-124 3-Cl,5-F CH2CF3 F Cl 4.121/352 [M-100]+ 151170.doc -56- 201127285 No. Rn R1 R2 R3 Physical Data (HPLC: RT[ Min]/m/z) 1-125 3-F CH2OCH3 F Cl 3.432/401 [M+Na]+ 1-126 3-N〇2 ch3 F Cl 3.493/399 [M+Na]+ 1-127 3- 1 ch3 F Cl 3.870/477 [M+H]+ 1-128 4-1 ch3 F Cl 3.751/458 [M+H]+ 1-129 3-1 HF Cl 3.290/466 [M+Na]+ 1- 130 4-1 HF Cl 3.347/466 [M+Na]+ 1-131 3-NH2 ch3 F Cl 2.479/347 [M+H]+ 1-132 3-NHCHO ch3 F Cl 2.883/376 [M+H] + 1-133 4-F ch2ch=ch-cooch3 F Cl 3.504/434 [M+H]+ 1-134 4-F (£)CH2CH=CH-C^CH F Cl 3.641/422 [M+39]+ 1-135 4-F (Z)CH2CH=CC1CH3 F Cl 3.863/424 [M+Hf 1-136 4-F ch2ch=c(ch3)2 F Cl 3.892/426 [M+Na]+ 1-137 4- F ch2ch=cci2 F Cl 3.466/445 [M+Na]+ 1-138 4-F (6) ch2ch=chcf3 F Cl 3.373/466 [M+Na]+ 1-139 4-F (Z)CH2CH=CHCH3 F Cl 3.874/412 [M+Na]+ 1-140 4-F CH2CH2F F Cl 3.482/404 [M+Na]+ 1-141 3,5-F2 CH2CH2F F Cl 3.545/422 [M+Na]+ 1-142 4-F 〇E)CH2CH=CHCH3 F Cl 3.848/412 [M+Na]+ 1-143 4-F ch3 F cf3 3.766/406 [M+Na]+ 1-144 4-F ch2c=ch F cf3 3.71 /430 [M+Na]+ 1-145 4-F ch3 F CN 1-146 4-F ch2och F CN 3.627/365 [M+H]+ 1-147 4-F ch3 FN〇2 3.317/383 [M +Na]+ 1-148 4-F ch3 F ocf3 3.656/432 [M+Na]+ 1-149 4-FHF cf3 3.363/392 [M+Na]+ 1-150 4-F ch3 F ch3 3.839/330 [M+H]+ 1-151 3-F,4-Cl ch3 F CN 3.931/384 [M+9]+ 1-152 3-F,4-Cl ch3 FN〇2 3.699/417 [M+Na] + 1-153 4-C1 ch3 F CN 3.541/357 [M+H]+ 1-154 4-F ch3 F chf2 3.608/343 [M-23]+ 1-155 4-FHF CN 2.813/326 [M+ H]+ 1-156 4-FHFN〇2 2.937/363 [M+18]+ 1-157 4-F ch3 FI 3.622/459 [M+18]+ g 151170.doc -57- 201127285 No. R„ R1 R2 R3 Physical Data (HPLC: RT [min]/m/z) 1-158 3,4-F2 ch3 FI 3.676/477 [M+18]+ 1-159 3,4,5-F3 ch3 FI 3.777/477 [ M+18]+ 1-160 3-CN ch3 FI 3.557/438 [M-10]+ 1-161 3-CN ch3 F Br 3.333/420 [M+19]+ 1-162 4-C1 ch3 F N02 3.649 /399 [M+Na]+ 1-163 4-Cl,3,5-F2 ch3 FN〇2 3.619/437 [M+Na]+ 1-164 4-Cl,3,5-F2 ch3 F CN 3.724/ 394 [M+Na]+ 1 -165 4-F ch3 F 2-F- C6H4 3.809/409 [M]+ 1-166 4-F ch3 F 3- cf3- C6H4 4.046/359 [M]+ 1-167 4-F ch3 F 3,4 ,5- f3- c6h2 3.988/445 [M]+ 1-168 4-F ch3 F 4-F- C6H4 3.838/409 [M]+ 1-169 4-F ch3 F c6h5 3.822/391 [M]+ 1 -170 4-F ch3 F 3-F- C6H4 3.849/409 [M]+ 1-171 4-FHF Br 3.214/362 [M-18]+ 1-172 4-F CH2CHF2 F Br 3.805/452 [M+ 8]+ 1-173 4-F ch2cf3 F Br 3.943/452 [M-10]+ 1-174 4-F ch2c=ch F Br 3.741/364 [M-54]+ 1-175 4-C1 ch3 F Br 3.842/412 [M+2]+ 1-176 3-FHF Br 3.198/382 [M+2]+ 1-177 3-CN HF Br 2.920/387 [M]+ 1-178 3,4-F2 HF Br 3.290/398 [M]+ 1-179 3,4,5-F3 HF Br 3.346/416 [M]+ 1-180 3,5-F2 HF Br 3.246/382 [M-16]+ 1-181 4- C1 HF Br 3.406/398 [M+2]+ 1-182 4-FHF chf2 2.794/374 [M+Na]+ 1-183 4-F CH2CF3 F chf2 3.257/456 [M+Na]+ 1-184 4 -F CH2OCH3 F chf2 3.450/396 [M+H]+ 1-185 4-F ch3 cf3 Cl 4.005/422 [M+H]+ 151170.doc •58- 201127285

編號 Rn R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-186 4-F CH2CHF2 F Br 3.805/452 [M+8]+ 1-187 4-F CH2CF3 F Br 3.943/452 [M-10]+ 1-188 4-F CH2CHF2 Br F 3.577/468 [M+Na]+ 1-189 4-F CH2CF3 Br F 3.732/484 [M+Na]+ 1-190 4-C1 CH2CHF2 Br F 3.981/484 [M+Na]+ 1-191 3,4-F2 CH2CHF2 Br F 3.855/484 [M+Na]+ 1-192 4-F CH2CH2F F Cl 3.482/404 [M+Na]+ 1-193 3,5-F2 CH2CH2F F Cl 3.545/422 [M+Na]+ 1-194 4-F CH2CF3 F chf2 3.257/456 [M+Na]+ 1-195 3,4-F2 CH2CHF2 Cl F 3.756/336 [M+18]+ 1-196 3,4-F2 ch2cf3 Cl F 3.906/454 [M+18]+ 1-197 3,5-F2 CH2CHF2 Cl F 3.757/435 [M+17]+ 1-198 3,5-F2 ch2cf3 Cl F 3.909/453 [M+17]+ 1-199 3,4,5-F3 CH2CHF2 Cl F 3.847/436 [M+H]+ 1-200 3,4,5-Fs CH2CF3 Cl F 3.994/476 [M+Na]+ 1-201 - CH2CHF2 Cl F 3.428/405 [M+Na]+ 1-202 CH2CF3 Cl F 3.582/422 [M+Na]+ 1-203 3-CN ch2chf2 Cl F 3.245/429 [M+Na]+ 1-204 3-CN CH2CF3 Cl F 3.402/447 [M+Na]+ 1-205 3-F CH2CHF2 Cl F 3.449/422 [M+Na]+ 1-206 3-F CH2CF3 Cl F 3.604/440 [M+Na]+ 1-207 4-C1 CH2CHF2 Cl F 3.613/439 [M+Na]+ 1-208 4-C1 CH2CF3 Cl F 3.765/456 [M+Na]+ 1-209 4-F CH2CH2CF3 F Cl 3.735/317 [M-114]+ 1-210 4-F CH2(2-F-C6H4) F Cl 3.957/466 [M+Na]+ 1-211 4-F CH2(2,6-F2-C6H3) F Cl 3.939/484 [M+Na]+ 1-212 4-F CH2(2,4-F2-C6H3) F Cl 3.966/484 [M+Na]+ 1-213 4-F CH2(2,5-F2-C6H3) F Cl 4.072/462 [M+H]+ 1-214 3-CN CH2(2,5-F2-C6H3) F Cl 3.712/468 [M+H]+ 1-215 3,4-F2 CH2(2,5-F2-C6H3) F Cl 3.937/501 [M+22]+ 1-216 4-C1 CH2OCH3 Cl F 3.576/418 [M+Na]+ 1-217 4-F H Cl F 3.202/358 [M+Na]+ 1-218 4-F H Cl F 2.983/336 [M+H]+ S 151170.doc -59- 201127285 編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-219 2,6-F2 H F Cl 2.893/354 [M+H]+ 1-220 2,3-F2 H F Cl 3.037/336 [M-18]+ 1-221 2,4-F2 H F Cl 3.031/354 [M+H]+ 1-222 2,5-F2 H F Cl 2.999/376 [M+Na]+ 1-223 2,4,6-F3 H F Cl 3.402/394 [M+Na]+ 1-224 2,3,6-F3 H F Cl 3.275/372 [M+H]+ 1-225 - CH2CHF2 Cl Cl 3.94/415 [M+17]+ 1-226 4-F CH2CH2CH3 F Cl 4.124/395 [M+18]+ 1-227 4-F CH2CH2CH2CH3 F Cl 3.402/409 [M+18]+ 1-228 3,4,5-F3 ch3 Br Br 4.164/492 [M+H]+ 1-229 3-F ch3 Br Br 3.944/456 [M+H]+ 1-230 3-CN ch3 Br Br 3.739/463 [M+H]+ 1-231 4-F ch3 Br Br 3.733/487 [M+Na]+ 1-232 - ch3 Br Br 4.002/460 [M+Na]+ 1-233 3,4-F2 ch3 Br Br 4.075/474 [M+H]+ 1-234 3,5-F2 ch3 Br Br 4.078/474 [M+H]+ 1-235 3,4,5-F3 H Br Br 3.683/500 [M+Na]+ 1-236 3-F H Br Br 3.488/464 [M+Na]+ 1-237 3-CN H Br Br 3.242/471 [M+Na]+ 1-238 4-F H Br Br 3.492/464 [M+Na]+ 1-239 - H Br Br 3.463/424 [M+H]+ 1-240 3,4-F2 H Br Br 3.565/482 [M+Na]+ 1-241 3,5-F2 H Br Br 3.578/482 [M+Na]+ 1-242 3,5-F2 H Cl Br 4.005/430 [M+H]+ 1-243 3,4-F2 ch3 Cl Br 3.999/430 [M+H]+ 1-244 3,4,5-F3 ch3 Cl Br 4.106/470 [M+Na]+ 1-245 3-F ch3 Cl Br 3.936/412 [M+H]+ 1-246 3-CN ch3 Cl Br 3.678/419 [M+H]+ 1-247 4-F ch3 Cl Br 3.908/434 [M+Na]+ 1-248 - ch3 Cl Br 3.868/411 [M+Na]+ 1-249 3,4-F2 H F chf2 3.953/370 [M+H]+ 1-250 3,4,5-F3 H F chf2 3.436/368 [M-19]+ 1-251 3,4-F2 CH2CF3 F chf2 3.446/472 [M+Na]+ 151170.doc -60- 201127285 編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-252 3-F H F chf2 3.015/352 [M+H]+ 1-253 3,4,5-F3 CH2CF3 F chf2 3.446/474 [M+Na]+ 1-254 3-F CH2CF3 F chf2 3.890/456 [M+Na]+ 1-255 3,5-F2 H Cl Br 3.512/438 [M+Na]+ 1-256 3,4-F2 H Cl Br 3.504/438 [M+Na]+ 1-257 3,4,5-Fs H Cl Br 3.62/456 [M+Na]+ 1-258 3-F H Cl Br 3.422/420 [M+Na]+ 1-259 3-CN H Cl Br 3.202/427 [M+Na]+ 1-260 - H Cl Br 3.358/402 [M+Na]+ 1-261 4-F H Cl Br 3.42/420 [M+Na]+ 1-262 4-F 4-F-QH4 F Cl 3.098/452 [M+Na]+ 1-263 4-F 3,5-F2-C6H3 F Cl 4.016/465 [M+18]+ 1-264 4-F 2,5-F2-C6H3 F Cl 3.936/462 [M+H]+ 1-265 4-F 2,3-F2-C6H3 F Cl 3.975/462 [M+H]+ 1-266 4-F 4-Cl-C6H4 F Cl 4.081/468 [M+Na]+ 1-267 4-F 2-Cl-C6H4 F Cl 3.997/465 [M+19]+ 1-268 4-F 3-Cl-C6H4 F Cl 4.079/465 [M+19]+ 1-269 4-F 2,4-Cl2-C6H3 F Cl 4.236/497 [M+17]+ 1-270 4-F 2,6-Cl2-C6H3 F Cl 4.126/499 [M+18]+ 1-271 4-F 2,5-Cl2-C6H3 F Cl 4.192/504 [M+Na]+ 1-272 4-F 3,5-Cl2-C6H3 F Cl 4.332/497 [M+17]+ 1-273 4-F 2,4,6-Cl3-C6H2 F Cl 4.407/533 [M+18]+ 1-274 4-F ch2-c6h5 F Cl 3.959/426 [M+H]+ 1-275 4-F CH2CH2CH3 F Cl 3.851/378 [M+H]+ 1-276 4-F CH2CCI3 F Cl 4.054/486 [M+18]+ 1-277 4-F CH2CHCI2 F Cl 3.985/456 [M+Na]+ 1-278 3,5-F2 ch3 F chf2 3.676/406 [M+Na]+ 1-279 3,5-F2 H F chf2 3.247/370 [M+H]+ 1-280 3,5-F2 CH2CF3 F chf2 3.917/474 [M+H]+ 1-281 4-F CH2OCH3 F Br 3.723/426 [M+2]+ 1-282 3-CN ch3 F Br 3.515/368 [M-33]+ 1-283 3-CN ch2och F Br 3.614/424 [M-H]+ 1-284 3-CN CH2CF3 F Br 3.834/485 [M+16]+ 151170.doc •61 - 201127285 編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-285 3-CN CH2CHF2 F Br 3.667/467 [M+16]+ 1-286 3-CN CH2OCH3 F Br 3.543/449 [M+18]+ 1-287 2,4-F2 CH2OCH3 F Cl 3.76/398 [M+H]+ 1-288 2,5-F2 CH2OCH3 F Cl 3.719/398 [M+H]+ 1-289 3-OCHb ch3 F Cl 3.604/330 [M-31]+ 1-290 3-CH3 ch3 F Cl 3.788/314 [M-31]+ 1-291 4-OCH3 ch3 F Cl 3.598/384 [M+Na]+ 1-292 3,5-(OCH3]2 ch3 F Cl 3.629/392 [M+H]+ 1-293 - ch2och F Br 3.716/421 [M+21]+ 1-294 - ch2cf3 F Br 3.938/467 [M+Na]+ 1-295 - CH2CHF2 F Br 3.777/447 [M+21]+ 1-296 - CH20CH3 F Br 3.646/429 [M+Na]+ 1-297 3,5-F2 ch3 F cf3 3.804/402 [M+H]+ 1-298 3,4-F2 ch3 F cf3 3.772/402 [M+H]+ 1-299 3,4,5-F3 ch3 F cf3 3.868/420 [M+H]+ 1-300 3-F ch3 F cf3 3.739/406 [M+Na]+ 1-301 3-CN ch3 F cf3 3.507/391 [M+H]+ 1-302 - ch3 F cf3 3.716/388 [M+Na]+ 1-303 3,5_F2 H F cf3 3.402/410 [M+Na]+ 1-304 3,4-F2 H F cf3 3.402/410 [M+Na]+ 1-305 3,4,5-F3 H F cf3 3.509/428 [M+Na]+ 1-306 3-F H F cf3 3.327/392 [M+Na]+ 1-307 3-CN H F cf3 3.125/399 [M+Na]+ 1-308 - H F cf3 3.283/399 [M+Na]+ 1-309 3-OCH3 H F Cl 3.148/330 [M-17]+ 1-310 3-CH3 H F Cl 3.325/354 [M+Na]+ 1-311 4-OCH3 H F Cl 3.135/370 [M+Na]+ 1-312 2,4-F2 CH2C=CH F Cl 3.752/392 [M+H]+ 1-313 2,4-F2 CH2CHF2 F Cl 3.799/440 [M+Na]+ 1-314 2,4-F2 CH2CF3 F Cl 3.959/458 [M+H]+ 1-315 2,5-F2 ch2och F Cl 3.705/392 [M+H]+ 1-316 2,5-F2 CH2CHF2 F Cl 3.75/440 [M+Na]+ 1-317 2,5-F CH2CF3 F Cl 3.916/458 [M+Na]+ 151170.doc -62- 201127285 編號 R„ R1 R2 R3 物理數據 (HPLC: RT[min]/m/z) 1-318 4-F CH2CH2CI F Cl 3.838/406 [M+Na]+ 1-319 3,4,5-F3 CH2OCH3 F Br 3.843/483 [M+Na]+ 1-320 3-F ch3 F chf2 3.502/388 [M+Na]+ 1-321 3,4,5-F3 ch2c=ch F Br 3.901/475 [M+21]+ 1-322 3,4,5-F3 CH2CF3 F Br 4.085/399 [M-99]+ 1-323 3,4,5-F3 ch2chf2 F Br 3.94/501 [M+21]+ 1-324 4-F ch2p(=o)(och2ch3)2 F Cl 3.549/486 [M+H]+ 1-325 4-F CH2(^)CH=CH(CH3)CH2 ch2ch=ch(ch3)2 F Cl 4.700/102 [M-369]+ 1-326 3-CN ch3 F chf2 3.280/395 [M+Na]+ 1-327 3-CN H F chf2 2.892/359 [M+H]+ 1-328 - ch3 F chf2 3.497/326 [M-18]+ 1-329 - H F chf2 3.074/351 [M+18]+ 1-330 4-F ch2ch2ch(ch3)ch2 ch2ch=ch(ch3)2 F Cl 4.835/139 [M-334]+ 1-331 3,4-F2 ch2och F Br 3.758/457 [M+21]+ 1-332 3,4-F2 CH2CF3 F Br 3.956/379 [M-101]+ 1-333 3,4-F2 CH2CHF2 F Br 3.812/483 [M+21]+ 1-334 3-F ch2c=ch F Br 3.69/361 [M-57]+ 1-335 3-F CH2CF3 F Br 3.895/361 [M-101]+ 1-336 3,5-F2 CH2CF3 F Br 3.953/550 [M+70]+ 1-337 3,5-F2 CH2CHF2 F Br 3.809/483 [M+21]+ 1-338 3-CN-5-F ch2chf2 F Br 3.648/397 [M-23]+ 1-339 3,5-F2 ch2och F Br 3.743/465 [M+21]+ 1-340 3-F CH2CHF2 F Br 3.306/380 [M+H]+ 1-341 4-F CH2CH20H F Cl 3.907/314 [M-31]+ 1-342 4-CH3 ch3 F Cl 3.790/314 [M-31]+ 1-343 4-F 2-FQH4 F Cl 3.896/429 [M+18]+ 使用實例 藉由以下溫室實驗證明式I化合物之除草活性： 所用培養容器為塑膠花盆，其含有約3.0%腐植質作為基 質的壤質^ 土。分別對各物種之測試植物的種子進行播 s 151170.doc -63- 201127285 種。 為進行出苗前處理，播種之後藉助於精細分佈喷嘴直接 施用已懸浮或乳化於水中之活性化合物。輕輕地灌溉容器 以促進發芽及生長’且隨後用透明塑膠罩覆蓋直至植物生 根。除非受到活性化合物之損傷’否則此覆蓋使測試植物 均勻發芽。 為進行出苗後處理’視植物習性而定’首先使測試植物 生長至3至15 cm之高度，且隨後用已懸浮或乳化於水中之 活性化合物處理。為此目的，將測試植物直接播種且使其 生長於相同容器中’或首先使其單獨生長為幼苗，且在處 理之前數日移植至測試容器中。 視物種而定，將植物保持在10_25。(：或2〇_35£>(：：下。測試 時段延續2至4週。在此期間，對植物進行照護且評估其對 個別處理之反應》 使用〇至1〇〇之等級進行評估。100意謂植物未出苗或 至少地表以上部分被完全破壞’且〇意謂無損傷，或正常 生長過程。在值為至少70時提供優良除草活性，且在值為 至少85時提供極佳除草活性。 溫室實驗中所用植物具有以下物種：No. Rn R1 R2 R3 Physical Data (HPLC: RT [min]/m/z) 1-186 4-F CH2CHF2 F Br 3.805/452 [M+8]+ 1-187 4-F CH2CF3 F Br 3.943/452 [ M-10]+ 1-188 4-F CH2CHF2 Br F 3.577/468 [M+Na]+ 1-189 4-F CH2CF3 Br F 3.732/484 [M+Na]+ 1-190 4-C1 CH2CHF2 Br F 3.981/484 [M+Na]+ 1-191 3,4-F2 CH2CHF2 Br F 3.855/484 [M+Na]+ 1-192 4-F CH2CH2F F Cl 3.482/404 [M+Na]+ 1-193 3,5-F2 CH2CH2F F Cl 3.545/422 [M+Na]+ 1-194 4-F CH2CF3 F chf2 3.257/456 [M+Na]+ 1-195 3,4-F2 CH2CHF2 Cl F 3.756/336 [ M+18]+ 1-196 3,4-F2 ch2cf3 Cl F 3.906/454 [M+18]+ 1-197 3,5-F2 CH2CHF2 Cl F 3.757/435 [M+17]+ 1-198 3, 5-F2 ch2cf3 Cl F 3.909/453 [M+17]+ 1-199 3,4,5-F3 CH2CHF2 Cl F 3.847/436 [M+H]+ 1-200 3,4,5-Fs CH2CF3 Cl F 3.994/476 [M+Na]+ 1-201 - CH2CHF2 Cl F 3.428/405 [M+Na]+ 1-202 CH2CF3 Cl F 3.582/422 [M+Na]+ 1-203 3-CN ch2chf2 Cl F 3.245 /429 [M+Na]+ 1-204 3-CN CH2CF3 Cl F 3.402/447 [M+Na]+ 1-205 3-F CH2CHF2 Cl F 3.449/422 [M+Na]+ 1-206 3-F CH2CF3 Cl F 3.604/440 [M+Na]+ 1-207 4-C1 CH2CHF2 Cl F 3.613/439 [M+Na]+ 1-20 8 4-C1 CH2CF3 Cl F 3.765/456 [M+Na]+ 1-209 4-F CH2CH2CF3 F Cl 3.735/317 [M-114]+ 1-210 4-F CH2(2-F-C6H4) F Cl 3.957/466 [M+Na]+ 1-211 4-F CH2(2,6-F2-C6H3) F Cl 3.939/484 [M+Na]+ 1-212 4-F CH2(2,4-F2- C6H3) F Cl 3.966/484 [M+Na]+ 1-213 4-F CH2(2,5-F2-C6H3) F Cl 4.072/462 [M+H]+ 1-214 3-CN CH2(2, 5-F2-C6H3) F Cl 3.712/468 [M+H]+ 1-215 3,4-F2 CH2(2,5-F2-C6H3) F Cl 3.937/501 [M+22]+ 1-216 4 -C1 CH2OCH3 Cl F 3.576/418 [M+Na]+ 1-217 4-FH Cl F 3.202/358 [M+Na]+ 1-218 4-FH Cl F 2.983/336 [M+H]+ S 151170 .doc -59- 201127285 No. R„ R1 R2 R3 Physical Data (HPLC: RT[min]/m/z) 1-219 2,6-F2 HF Cl 2.893/354 [M+H]+ 1-220 2, 3-F2 HF Cl 3.037/336 [M-18]+ 1-221 2,4-F2 HF Cl 3.031/354 [M+H]+ 1-222 2,5-F2 HF Cl 2.999/376 [M+Na ]+ 1-223 2,4,6-F3 HF Cl 3.402/394 [M+Na]+ 1-224 2,3,6-F3 HF Cl 3.275/372 [M+H]+ 1-225 - CH2CHF2 Cl Cl 3.94/415 [M+17]+ 1-226 4-F CH2CH2CH3 F Cl 4.124/395 [M+18]+ 1-227 4-F CH2CH2CH2CH3 F Cl 3.402/409 [M+18]+ 1-228 3 ,4,5-F3 ch3 Br Br 4.164/492 [M+H]+ 1-229 3-F ch3 Br Br 3.944/456 [M+H]+ 1-230 3-CN ch3 Br Br 3.739/463 [M+H]+ 1-231 4-F ch3 Br Br 3.733/487 [M+Na] + 1-232 - ch3 Br Br 4.002/460 [M+Na]+ 1-233 3,4-F2 ch3 Br Br 4.075/474 [M+H]+ 1-234 3,5-F2 ch3 Br Br 4.078/ 474 [M+H]+ 1-235 3,4,5-F3 H Br Br 3.683/500 [M+Na]+ 1-236 3-FH Br Br 3.488/464 [M+Na]+ 1-237 3 -CN H Br Br 3.242/471 [M+Na]+ 1-238 4-FH Br Br 3.492/464 [M+Na]+ 1-239 - H Br Br 3.463/424 [M+H]+ 1-240 3,4-F2 H Br Br 3.565/482 [M+Na]+ 1-241 3,5-F2 H Br Br 3.578/482 [M+Na]+ 1-242 3,5-F2 H Cl Br 4.005/ 430 [M+H]+ 1-243 3,4-F2 ch3 Cl Br 3.999/430 [M+H]+ 1-244 3,4,5-F3 ch3 Cl Br 4.106/470 [M+Na]+ 1 -245 3-F ch3 Cl Br 3.936/412 [M+H]+ 1-246 3-CN ch3 Cl Br 3.678/419 [M+H]+ 1-247 4-F ch3 Cl Br 3.908/434 [M+ Na]+ 1-248 - ch3 Cl Br 3.868/411 [M+Na]+ 1-249 3,4-F2 HF chf2 3.953/370 [M+H]+ 1-250 3,4,5-F3 HF chf2 3.436/368 [M-19]+ 1-251 3,4-F2 CH2CF3 F chf2 3.446/472 [M+Na]+ 151170.doc -60- 201127285 No. R„ R1 R2 R3 Physical data (HPLC: RT[min ]/m/z) 1-252 3-FHF c Hf2 3.015/352 [M+H]+ 1-253 3,4,5-F3 CH2CF3 F chf2 3.446/474 [M+Na]+ 1-254 3-F CH2CF3 F chf2 3.890/456 [M+Na]+ 1-255 3,5-F2 H Cl Br 3.512/438 [M+Na]+ 1-256 3,4-F2 H Cl Br 3.504/438 [M+Na]+ 1-257 3,4,5-Fs H Cl Br 3.62/456 [M+Na]+ 1-258 3-FH Cl Br 3.422/420 [M+Na]+ 1-259 3-CN H Cl Br 3.202/427 [M+Na]+ 1-260 - H Cl Br 3.358/402 [M+Na]+ 1-261 4-FH Cl Br 3.42/420 [M+Na]+ 1-262 4-F 4-F-QH4 F Cl 3.098/452 [M+Na ]+ 1-263 4-F 3,5-F2-C6H3 F Cl 4.016/465 [M+18]+ 1-264 4-F 2,5-F2-C6H3 F Cl 3.936/462 [M+H]+ 1-265 4-F 2,3-F2-C6H3 F Cl 3.975/462 [M+H]+ 1-266 4-F 4-Cl-C6H4 F Cl 4.081/468 [M+Na]+ 1-267 4 -F 2-Cl-C6H4 F Cl 3.997/465 [M+19]+ 1-268 4-F 3-Cl-C6H4 F Cl 4.079/465 [M+19]+ 1-269 4-F 2,4- Cl2-C6H3 F Cl 4.236/497 [M+17]+ 1-270 4-F 2,6-Cl2-C6H3 F Cl 4.126/499 [M+18]+ 1-271 4-F 2,5-Cl2- C6H3 F Cl 4.192/504 [M+Na]+ 1-272 4-F 3,5-Cl2-C6H3 F Cl 4.332/497 [M+17]+ 1-273 4-F 2,4,6-Cl3- C6H2 F Cl 4.407/533 [M+18]+ 1-274 4-F ch2-c6h5 F Cl 3.959/426 [M+H]+ 1-275 4-F CH2CH2CH3 F Cl 3.851/ 378 [M+H]+ 1-276 4-F CH2CCI3 F Cl 4.054/486 [M+18]+ 1-277 4-F CH2CHCI2 F Cl 3.985/456 [M+Na]+ 1-278 3,5- F2 ch3 F chf2 3.676/406 [M+Na]+ 1-279 3,5-F2 HF chf2 3.247/370 [M+H]+ 1-280 3,5-F2 CH2CF3 F chf2 3.917/474 [M+H ]+ 1-281 4-F CH2OCH3 F Br 3.723/426 [M+2]+ 1-282 3-CN ch3 F Br 3.515/368 [M-33]+ 1-283 3-CN ch2och F Br 3.614/424 [MH]+ 1-284 3-CN CH2CF3 F Br 3.834/485 [M+16]+ 151170.doc •61 - 201127285 No. R„ R1 R2 R3 Physical Data (HPLC: RT[min]/m/z) 1 -285 3-CN CH2CHF2 F Br 3.667/467 [M+16]+ 1-286 3-CN CH2OCH3 F Br 3.543/449 [M+18]+ 1-287 2,4-F2 CH2OCH3 F Cl 3.76/398 [ M+H]+ 1-288 2,5-F2 CH2OCH3 F Cl 3.719/398 [M+H]+ 1-289 3-OCHb ch3 F Cl 3.604/330 [M-31]+ 1-290 3-CH3 ch3 F Cl 3.788/314 [M-31]+ 1-291 4-OCH3 ch3 F Cl 3.598/384 [M+Na]+ 1-292 3,5-(OCH3]2 ch3 F Cl 3.629/392 [M+H ]+ 1-293 - ch2och F Br 3.716/421 [M+21]+ 1-294 - ch2cf3 F Br 3.938/467 [M+Na]+ 1-295 - CH2CHF2 F Br 3.777/447 [M+21]+ 1-296 - CH20CH3 F Br 3.646/429 [M+Na]+ 1-297 3,5-F2 ch3 F cf3 3.804/4 02 [M+H]+ 1-298 3,4-F2 ch3 F cf3 3.772/402 [M+H]+ 1-299 3,4,5-F3 ch3 F cf3 3.868/420 [M+H]+ 1 -300 3-F ch3 F cf3 3.739/406 [M+Na]+ 1-301 3-CN ch3 F cf3 3.507/391 [M+H]+ 1-302 - ch3 F cf3 3.716/388 [M+Na] + 1-303 3,5_F2 HF cf3 3.402/410 [M+Na]+ 1-304 3,4-F2 HF cf3 3.402/410 [M+Na]+ 1-305 3,4,5-F3 HF cf3 3.509 /428 [M+Na]+ 1-306 3-FHF cf3 3.327/392 [M+Na]+ 1-307 3-CN HF cf3 3.125/399 [M+Na]+ 1-308 - HF cf3 3.283/399 [M+Na]+ 1-309 3-OCH3 HF Cl 3.148/330 [M-17]+ 1-310 3-CH3 HF Cl 3.325/354 [M+Na]+ 1-311 4-OCH3 HF Cl 3.135/ 370 [M+Na]+ 1-312 2,4-F2 CH2C=CH F Cl 3.752/392 [M+H]+ 1-313 2,4-F2 CH2CHF2 F Cl 3.799/440 [M+Na]+ 1 -314 2,4-F2 CH2CF3 F Cl 3.959/458 [M+H]+ 1-315 2,5-F2 ch2och F Cl 3.705/392 [M+H]+ 1-316 2,5-F2 CH2CHF2 F Cl 3.75/440 [M+Na]+ 1-317 2,5-F CH2CF3 F Cl 3.916/458 [M+Na]+ 151170.doc -62- 201127285 No. R„ R1 R2 R3 Physical Data (HPLC: RT[min ]/m/z) 1-318 4-F CH2CH2CI F Cl 3.838/406 [M+Na]+ 1-319 3,4,5-F3 CH2OCH3 F Br 3.843/483 [M+Na]+ 1-320 3 -F Ch3 F chf2 3.502/388 [M+Na]+ 1-321 3,4,5-F3 ch2c=ch F Br 3.901/475 [M+21]+ 1-322 3,4,5-F3 CH2CF3 F Br 4.085 /399 [M-99]+ 1-323 3,4,5-F3 ch2chf2 F Br 3.94/501 [M+21]+ 1-324 4-F ch2p(=o)(och2ch3)2 F Cl 3.549/486 [M+H]+ 1-325 4-F CH2(^)CH=CH(CH3)CH2 ch2ch=ch(ch3)2 F Cl 4.700/102 [M-369]+ 1-326 3-CN ch3 F chf2 3.280/395 [M+Na]+ 1-327 3-CN HF chf2 2.892/359 [M+H]+ 1-328 - ch3 F chf2 3.497/326 [M-18]+ 1-329 - HF chf2 3.074/ 351 [M+18]+ 1-330 4-F ch2ch2ch(ch3)ch2 ch2ch=ch(ch3)2 F Cl 4.835/139 [M-334]+ 1-331 3,4-F2 ch2och F Br 3.758/457 [M+21]+ 1-332 3,4-F2 CH2CF3 F Br 3.956/379 [M-101]+ 1-333 3,4-F2 CH2CHF2 F Br 3.812/483 [M+21]+ 1-334 3 -F ch2c=ch F Br 3.69/361 [M-57]+ 1-335 3-F CH2CF3 F Br 3.895/361 [M-101]+ 1-336 3,5-F2 CH2CF3 F Br 3.953/550 [M +70]+ 1-337 3,5-F2 CH2CHF2 F Br 3.809/483 [M+21]+ 1-338 3-CN-5-F ch2chf2 F Br 3.648/397 [M-23]+ 1-339 3 ,5-F2 ch2och F Br 3.743/465 [M+21]+ 1-340 3-F CH2CHF2 F Br 3.306/380 [M+H]+ 1-341 4-F CH2CH20H F Cl 3.907/314 [M-31 ]+ 1-342 4- CH3 ch3 F Cl 3.790/314 [M-31]+ 1-343 4-F 2-FQH4 F Cl 3.896/429 [M+18]+ Example of Use The following greenhouse experiments demonstrate the herbicidal activity of the compound of formula I: The container is a plastic flower pot containing about 3.0% humus as a substrate for the loam soil. The seeds of the test plants of each species were separately sown 151170.doc -63- 201127285 species. For pre-emergence treatment, the active compound which has been suspended or emulsified in water is applied directly after sowing by means of a finely distributed nozzle. Gently irrigate the container to promote germination and growth' and then cover with a clear plastic cover until the plant roots. This coverage causes the test plants to germinate evenly unless damaged by the active compound. For post-emergence treatment 'depending on plant habits', the test plants are first grown to a height of 3 to 15 cm and subsequently treated with the active compound which has been suspended or emulsified in water. For this purpose, the test plants are directly sown and grown in the same container' or first grown separately into seedlings and transplanted into the test container several days prior to treatment. Depending on the species, keep the plants at 10-25. (: or 2〇_35£>(::下. The test period lasts 2 to 4 weeks. During this period, the plants are cared for and their response to individual treatments is evaluated.) Evaluation is carried out using a scale of 〇 to 1〇〇 100 means that the plant has not emerged or at least the above part of the surface is completely destroyed 'and that means no damage, or normal growth process. Provides excellent herbicidal activity at a value of at least 70, and provides excellent weeding at a value of at least 85 The plants used in the greenhouse experiments have the following species:

Bayer代碼 通用名稱 ALOMY 大穗看麥娘(Alopecurus myosuroides) 黑草(blackgrass) AMARE 反枝莧(Amaranthus retroflexus) 反枝荒(carelessweed) AVEFA 燕麥草(Avena fatua) 燕麥草(spring wild-oat) GALAP 緒块缺(Galium aparine) 牛筋草(goosegrass) POLCO 卷莖蓼(Fallopia convolvulus) 卷莖蓼(bearbine) SETFA 法氏狗尾草(Setaria faberi) 大狗尾草(giant foxtail) SETVI 狗尾草(Setaria viridis) 狗尾草(green foxtail) 151170.doc -64 - 201127285 1) 藉由出芽後方法針對ALOMY施用，施用率為0.125 kg/ha之活性化合物1-263及施用率為0.25 kg/ha之活性化合 物1-296展示良好除草活性。 2) 藉由出芽後方法針對ALOMY施用，施用率為0.125 kg/ha或 0.130 kg/ha之活性化合物1-3、1-29、1-34、1-64、 I_71 、1-153、1-217、1-221、1-222、1-249、1-262、 1-303、1-304、1-308及 1-343及施用率為0.25 kg/ha之活性 化合物1-26、1-27、1-186、1-216、1-231、1-297、1-298、 I - 2 9 9及I - 3 0 0展.不極佳除草活性。 3) 藉由出芽後方法針對AMARE施用，施用率為0.125 kg/ha之活性化合物1-305及1-306展示良好除草活性。 4) 藉由出芽後方法針對AMARE施用，施用率為0.125 kg/ha之活性化合物 Ι·2、1-3、1-18、1-30、1-33 ' 1-34、 1-67、1-153、1-170、1-265、1-266、1-267、1-268、 1-269、1-271、1-272、Ι·274、1-275、1-307及 1-334及施用 率為 0.25 kg/ha之活性化合物 1-62、1-63、1-281、1-282、 1-283、1-284、1-285及1-286展示極佳除草活性。 5) 藉由出芽後方法針對AVEFA施用，施用率為〇,125 kg/ha之活性化合物Ι·22〇、1-265及1-271及施用率為0.250 kg/ha之活性化合物1-287及1-341展示良好除草活性。 6) 藉由出芽後方法針對AVEFA施用，施用率為〇」25 kg/ha或 0.130 kg/ha之活性化合物 1-18、1-29、1-33、1_64、 1-65、1-66、1-71、1-163、1-172、1-217、1-249、1-250、 1-251、1-226、1-249、1-251、1-252、1-253、1-254、 S-- -65- 151170.doc 201127285 1-255、1-264、1-266、1-267、1-268、1-269、1-272、 1-276、1-278、1-279、1-280.、1-331、1-332、1-333、 1-334、1-339及1-340及施用率為〇·25 kg/ha之活性化合物 1-26 ' 1-27、1-157、1-216、1-221、1-231、1-281、1-282、 1-283、1-284、1-285、1-286、1-288、1_293、1-294、 1-295、1-297、1-298、1-315、1-316、1-317、1-318、 1-319、1-320、1-321、1-322、1-323、1-324、1-326、 1-327、1-328、1-335、1-336及 1-337展示極佳除草活性。 7) 藉由出芽後方法針對CHEAL施用，施用率為0.125 kg/ha之活性化合物1-255及施用率為0.250 kg/ha之活性化 合物I - 3 4 2展示極佳除草活性。 8) 藉由出芽後方法針對GALAP施用，施用率為〇. 125 kg/ha之活性化合物 1-2、1-65、1-66、1-67、1-70、1-168、 1-17〇、1-172及1_277展示極佳除草活性。 9) 藉由出芽後方法針對P〇LCO施用，施用率為0.125 kg/ha 或 0.130 kg/ha之活性化合物 i_i8、1-220、1-238、 1-245、1-252、1-264及1-278展示良好除草活性，且活性化 合物 1-64、1-65 、1-66 、1-163、 1-166 ' 1-168、 1-170、 1-172、1-217、 1-221、 1-222、 1-226、 1-235、 1-237、 1-243、1-246、 1-250、 1-251、 1-253、 1-254、 1-256 > 1-259、1-262、 1-263、 1-274、 1-275 、 1-276、 1-277 、 1-279、1-280、1-329、1-331、1-332、1-333 及 1-343 展示極 佳除草活性。 10)藉由出芽後方法針對p〇LCl〇施用，施用率為0.25 151170.doc -66 - 201127285 kg/ha之活性化合物Ι·296展示良好除草活性，且活性化合 物1-216、1-231、1-273、1-287及1-299展示極佳除草活性。 11) 藉由出芽後方法針對SETFA施用，施用率為〇_125 kg/ha之活性化合物1-3 16展示良好除草活性。 12) 藉由出芽後方法針對SETFA施用，施用率為〇.125 kg/ha之活性化合物 1-303、1-304、1-305、1-306及 1-307及 施用率為0.25 kg/ha之活性化合物j-300、1_315、1-3 17及 1-31 8展示極佳除草活性。 13) 藉由出芽後方法針對sETVI施用，施用率為0.130 1^/1^之活性化合物1-3 09及施用率為0.25]^/}^之活性化合 物I-293、1-294及1-341展示良好除草活性。 14) 藉由出芽後方法針對SETVI施用，施用率為〇.125 kg/ha之活性化合物 ι·2、1-3、^0、133、134、167、 1-70、1-71、1-153、1-166、1-227、1-249、1-250、1-251 及 1-255及施用率為0.25 kg/ha之活性化合物1-62、1-63、 1-157、1-186、1-221、i_288、1-319、1-320、1-321、 1-322、1-323、1-324、1-326、1-327、1-328、1-335、1-336 及1-337展示極佳除草活性。Bayer code common name ALOMY Alopecurus myosuroides blackgrass AMARE Amaranthus retroflexus carelessweed AVEFA Avena fatua oat grass (spring wild-oat) GALAP Gallium aparine Goosegrass POLCO Ballopia convolvulus Bearbine SETFA Setaria faberi Big foxtail SETVI Setaria viridis Green foxtail 151170.doc -64 - 201127285 1) The active compound 1-261 with an application rate of 0.125 kg/ha and the active compound 1-296 with an application rate of 0.25 kg/ha exhibit good herbicidal activity by means of a post-emergence method for ALOMY administration. . 2) Active compound 1-3, 1-29, 1-34, 1-64, I_71, 1-153, 1- for application to ALOMY by post-emergence method at an application rate of 0.125 kg/ha or 0.130 kg/ha 217, 1-221, 1-222, 1-249, 1-262, 1-303, 1-304, 1-308 and 1-343 and active compounds 1-26, 1- with an application rate of 0.25 kg/ha 27, 1-186, 1-216, 1-231, 1-297, 1-198, I - 2 9 9 and I - 3 0 0 show. Not excellent herbicidal activity. 3) The active compounds 1-305 and 1-306 having an application rate of 0.125 kg/ha exhibited good herbicidal activity against AMARE by post-emergence method. 4) Active compound for application of AMARE by post-emergence method, application rate of 0.125 kg/ha Ι·2, 1-3, 1-18, 1-30, 1-33 ' 1-34, 1-67, 1 -153, 1-170, 1-265, 1-266, 1-267, 1-268, 1-269, 1-271, 1-172, Ι·274, 1-275, 1-307, and 1-334 The active compounds 1-62, 1-63, 1-281, 1-282, 1-283, 1-284, 1-285 and 1-286 with an application rate of 0.25 kg/ha exhibited excellent herbicidal activity. 5) Application to AVEFA by post-emergence method, application rate is 〇, 125 kg/ha of active compounds Ι·22〇, 1-265 and 1-271, and active compound 1-287 with an application rate of 0.250 kg/ha and 1-341 shows good herbicidal activity. 6) Application to AVEFA by post-emergence method, the application rate is 〇"25 kg/ha or 0.130 kg/ha of active compounds 1-18, 1-29, 1-33, 1-64, 1-65, 1-66, 1-71, 1-163, 1-172, 1-217, 1-249, 1-250, 1-251, 1-226, 1-249, 1-251, 1-252, 1-253, 1- 254, S---65- 151170.doc 201127285 1-255, 1-246, 1-266, 1-267, 1-268, 1-269, 1-172, 1-276, 1-278, 1- 279, 1-180., 1-331, 1-332, 1-333, 1-334, 1-339 and 1-340 and the active compound 1-26 ' 1-27 with an application rate of 〇·25 kg/ha , 1-157, 1-216, 1-221, 1-231, 1-281, 1-282, 1-283, 1-284, 1-285, 1-286, 1-288, 1-293, 1-294 , 1-295, 1-297, 1-198, 1-315, 1-316, 1-317, 1-318, 1-319, 1-320, 1-321, 1-322, 1-323, 1 -324, 1-326, 1-327, 1-328, 1-335, 1-336 and 1-37 show excellent herbicidal activity. 7) The active compound 1-255 having an application rate of 0.125 kg/ha and the active compound I - 4 2 2 having an application rate of 0.250 kg/ha exhibited excellent herbicidal activity against CHEAL by the post-emergence method. 8) Application to GALAP by post-emergence method, the application rate is 〇 125 kg / ha of active compounds 1-2, 1-65, 1-66, 1-67, 1-70, 1-168, 1-17 〇, 1-172 and 1_277 show excellent herbicidal activity. 9) The active compound i_i8, 1-220, 1-238, 1-245, 1-252, 1-246 and the application rate of 0.125 kg/ha or 0.130 kg/ha by the post-emergence method for P〇LCO administration 1-278 exhibits good herbicidal activity, and active compounds 1-64, 1-65, 1-66, 1-163, 1-166 ' 1-168, 1-170, 1-172, 1-217, 1-221 , 1-222, 1-226, 1-235, 1-237, 1-243, 1-246, 1-250, 1-251, 1-253, 1-254, 1-256 > 1-259, 1-262, 1-263, 1-274, 1-275, 1-276, 1-277, 1-279, 1-280, 1-329, 1-331, 1-332, 1-333 and 1- 343 shows excellent herbicidal activity. 10) Applying p〇LCl〇 by post-emergence method, the application rate of 0.25 151170.doc -66 - 201127285 kg/ha of active compound Ι·296 shows good herbicidal activity, and active compounds 1-216, 1-231, 1-273, 1-287 and 1-199 exhibit excellent herbicidal activity. 11) The active compound 1-3 16 applied at a rate of 〇 _ 125 kg/ha by the post-emergence method for SETFA showed good herbicidal activity. 12) Application to SETFA by post-emergence method, the application rate is 125.125 kg/ha of active compounds 1-303, 1-304, 1-305, 1-306 and 1-307 and the application rate is 0.25 kg/ha The active compounds j-300, 1-315, 1-3 17 and 1-31 8 exhibited excellent herbicidal activity. 13) The active compound 1-3 09 and the application rate of 0.25]^/}^ are applied to the sETVI by the post-emergence method, and the active compounds I-293, 1-194 and 1- 341 shows good herbicidal activity. 14) Application to SETVI by post-emergence method, the application rate is 125.125 kg/ha of active compounds ι·2, 1-3, ^0, 133, 134, 167, 1-70, 1-71, 1- 153, 1-166, 1-227, 1-249, 1-250, 1-251 and 1-255 and active compounds 1-62, 1-63, 1-157, 1- with an application rate of 0.25 kg/ha 186, 1-221, i_288, 1-319, 1-320, 1-321, 1-322, 1-323, 1-324, 1-326, 1-327, 1-328, 1-335, 1- 336 and 1-37 show excellent herbicidal activity.

S 151170.doc -67-S 151170.doc -67-

Claims (1)

201127285 七、申請專利範圍： 1. 一種式I之氰基丁酸化物化合物，201127285 VII. Patent application scope: 1. A cyanobutyrate compound of the formula I, 〇、 R1 其中代號具有以下含義： R 為函素；氰基；硝基；Ci-C4院·基；d-CU _境 基；c2-c6稀基；（：2-(：6块基；Z-三（CVC4燒基）石夕 烧基， Rl 為氫；Z-CN ; CVCs烧基；z-c3-c6m院基；（Vr 齒燒基；C3-C8烯基；Z-C3-C^烯基；c3-c8^ 基，Z-(三-C1-C4烧基）石夕燒基；Z-C( = 〇)-Ra . Z_p(=〇)(Ra)2 ; Z-苯基；含有1、2、3或4個選自 由〇、N及S組成之群之雜原子的3至7員單環或9 或W員雙環飽和、不飽和或芳族雜環，該雜環 可部分或完全經基團Ra及/或Rb取代且經由碳或 氮連， R 為氫；OH ; Ci-Cg烧基；（^-匸斗齒燒基； Z-C3_C6環烧基；CrC8均基；Z-C5-C6環烯 基；C 2 c 8 炔基；Z - C 1 - C 6 燒氧基；Z - c 1 - C 4 齒 燒氧基；Z-C3-C8烯氧基’ Z-C3-C8炔氧基； NRiRH ; CVC6烷基磺醯基；Z-(三_Cl_c4炫 151170.doc 201127285 基）矽貌基；Ζ·茉其· 7 ^•备甘 己本丞，Z-本乳基；z•苯基胺 或含有1、2、3或4個選自由Ο、N及S組 成之群之雜原子的5或6員單環或9或10員雙 雜展其中該等環狀基團未經取代或經 1、2、3或4個基團Rb取代； R R彼此獨立為氫；C】-C8烷基，· c丨-C4 齒燒基；C3-C8婦基；c3_c8炔基； Z-C3-C6環烷基；2<1_(：8烷氧基； z_c丨-c8齒烷氧基；z-C(=〇)-RA;其 中R、〇H或Ci-C4烧氧基； R1及R11與其所連接之氮原子一起亦 可能形成含有1、2、3或4個選自由 〇、N及S組成之群之雜原子的5或6 員單環或9或10員雙環雜環； Rb 彼此獨立為 Z-CN ; Z-OH ; Z-N02 ; Z-齒 素；C「C8烷基；c〗-C4鹵烷基；C2-C8烯基； c2-c8炔基；Z-C〗-C8烷氧基；Z-CVCs鹵烷氧 基；Z-C3-C1G環烷基；〇_Z-C3-Ch)環烷基； Z-C( = 〇)-Ra ; NRiRii ; Z•(三 _Cl_C4烧基）石夕烷 »bb 基：z-笨基及S(〇)mRl 其中R為Ci-Cg烧基或C!-C6函烧基，且 m為0、1或2 ; Rb與連接至相鄰碳原子之基團Rb—起亦可能形 成5或6員飽和或部分或完全不飽和環，該環除 151170.doc 201127285 碳原子以外亦可能含有1、2或3個選自由Ο、N 及S組成之群之雜原子； z為共價鍵或<^-(：8伸烷基； η 為〇、1、2、3、4或5; R ' R彼此獨立為鹵素；氰基；硝基；CVC4烷基；（VC4 烧氧基；S(0)mRbb ; NRiRii ; Ci_C4鹵烷基；Ci_c4 鹵烷氧基； 其中在該等基團尺及尺1及其取代基中，該等碳鏈及/或該 等環狀基團可部分或完全經基團Ra及/或Rb取代， 其限制條件為 a) 若n=〇且Ri為乙基，則R2及R3不 同時為氯；及 b) 若n=l或2 ’ Ri為甲基，r2為氟且R3為氟、氯或溴，則 R不為氟； 或其N-氧化物或農業上適合之鹽。 2.如請求項化合物，其中Ri不為曱基或乙基。 3·如請求項1之式I化合物，其中若R為曱基，則R2&R3不 同時為氯。 4. 如請求項1至3中任一項之式I化合物，其中R2及R3不同時 為風I。 5. 如請求項1至4中任一項之式I化合物，其中R2及r3為 2,5-F2、2-F，5-Cl、2-F，5-Br、2-F，5-CN、2-F，5-N〇2、 2-F，5-CF3、2-F，5-OCH3 或 2-Cl，5-F。 6. 如請求項1至5中任一項之式I化合物，其中R2為氟。 7. 如請求項1至6中任一項之式I化合物，其中R2及R3為氣。 s 151170.doc 201127285 8·如請求項1至7中任一項之式I化合物，其中R為氯、氟、 氰基或硝基，且該下標η之值為1、2或3。 9. 如請求項1至8中任一項之式I化合物，其中Rn&3_F、 3,4-F2、3,5-F2、3,4,5-F3、3-F，4-C 卜 4-Cn' 4-F 或 3-CN。 10. 如請求項1至9中任一項之式I化合物，其中R為氟且該下 標η之值為1。 11·如請求項1至1〇中任一項之式I化合物，其中r1為 ch2cn、ch2ch2f、CH2CHF2、CH2CF3、ch2och3 或 CH2CsCH。 12.如請求項1至11中任一項之式J化合物，其中R1為ch3。 13- —種製備如請求項1至12中任一項之式I化合物之方法， 其係根據邁克加成法（Michael addition)，使式π之笨基 乙腈衍生物〇, R1 where the code has the following meanings: R is a pheromone; cyano; nitro; Ci-C4 courtyard base; d-CU _ context; c2-c6 thin base; (: 2-(: 6 block; Z-tri (CVC4 alkyl), sulphur, Rl is hydrogen; Z-CN; CVCs; z-c3-c6m; (Vr dentate; C3-C8 alkenyl; Z-C3-C ^Alkenyl; c3-c8^ group, Z-(tri-C1-C4 alkyl) sulphuric acid; ZC(= 〇)-Ra. Z_p(=〇)(Ra)2 ; Z-phenyl; 1, 2, 3 or 4 3 to 7 membered monocyclic or 9 or W membered bicyclic saturated, unsaturated or aromatic heterocyclic rings selected from the group consisting of hydrazine, N and S, which may be partially or Substituted by groups Ra and/or Rb and bonded via carbon or nitrogen, R is hydrogen; OH; Ci-Cg alkyl; (^-匸 齿 烧; Z-C3_C6 cycloalkyl; CrC8 homo; Z -C5-C6 cycloalkenyl; C 2 c 8 alkynyl; Z - C 1 - C 6 alkoxy; Z - c 1 - C 4 alkoxy; Z-C3-C8 alkenyl 'Z-C3 -C8 alkynyloxy; NRiRH; CVC6 alkylsulfonyl; Z-(three_Cl_c4 炫151170.doc 201127285 base) 矽 基; Ζ·莫其·7 ^•备甘己本丞, Z-本乳Base; z•phenylamine or contains 1, 2, 3 or 4 a 5 or 6 membered monocyclic or 9 or 10 membered heteroatom of a hetero atom of a group consisting of free oximes, N and S, wherein the cyclic groups are unsubstituted or 1, 2, 3 or 4 groups Rb Substituting; RR is independently hydrogen; C]-C8 alkyl, · c丨-C4 dentate; C3-C8 cation; c3_c8 alkynyl; Z-C3-C6 cycloalkyl; 2 <1_(:8-alkane Oxy; z_c丨-c8-to-alkoxy; zC(=〇)-RA; wherein R, 〇H or Ci-C4 alkoxy; R1 and R11 together with the nitrogen atom to which they are attached may also form 1, 2 , 3 or 4, 5 or 6 membered monocyclic or 9 or 10 membered bicyclic heterocycles selected from the group consisting of hydrazine, N and S; Rb are independently of each other Z-CN; Z-OH; Z-N02; Z-dentate; C "C8 alkyl; c" - C4 haloalkyl; C2-C8 alkenyl; c2-c8 alkynyl; ZC-C8 alkoxy; Z-CVCs haloalkoxy; Z-C3 -C1Gcycloalkyl; 〇_Z-C3-Ch)cycloalkyl; ZC(= 〇)-Ra ; NRiRii ; Z•(tri-Cl_C4 alkyl) oxalate»bb base: z-stupid and S (〇)mRl wherein R is a Ci-Cg alkyl group or a C!-C6 functional group, and m is 0, 1 or 2; Rb may also form 5 or 6 with a group Rb attached to an adjacent carbon atom. Saturated or partially or completely not full And ring, which may contain 1, 2 or 3 heteroatoms selected from the group consisting of ruthenium, N and S in addition to the 151170.doc 201127285 carbon atom; z is a covalent bond or <^-(:8烷基 is 〇, 1, 2, 3, 4 or 5; R ' R is independently of each other halogen; cyano; nitro; CVC4 alkyl; (VC4 alkoxy; S(0)mRbb; NRiRii; Ci_C4 Haloalkyl; Ci_c4 haloalkoxy; wherein in the group and the sizing and its substituents, the carbon chains and/or the cyclic groups may be partially or completely via the group Ra and/or Rb substitution, the restriction condition is a) if n=〇 and Ri is ethyl, then R2 and R3 are not chlorine at the same time; and b) if n=l or 2 ' Ri is methyl, r2 is fluorine and R3 is fluorine , chlorine or bromine, then R is not fluorine; or its N-oxide or agriculturally suitable salt. 2. A compound of the claim wherein Ri is not decyl or ethyl. 3. A compound of formula I according to claim 1, wherein if R is a fluorenyl group, then R2&R3 is different from chlorine. 4. The compound of formula I according to any one of claims 1 to 3, wherein R2 and R3 are not simultaneously wind I. 5. The compound of formula I according to any one of claims 1 to 4, wherein R2 and r3 are 2,5-F2, 2-F, 5-Cl, 2-F, 5-Br, 2-F, 5- CN, 2-F, 5-N〇2, 2-F, 5-CF3, 2-F, 5-OCH3 or 2-Cl, 5-F. 6. A compound of formula I according to any one of claims 1 to 5 wherein R2 is fluoro. 7. The compound of formula I according to any one of claims 1 to 6, wherein R2 and R3 are a gas. The compound of formula I according to any one of claims 1 to 7, wherein R is chlorine, fluorine, cyano or nitro, and the value of the subscript η is 1, 2 or 3. 9. The compound of formula I according to any one of claims 1 to 8, wherein Rn&3_F, 3,4-F2, 3,5-F2, 3,4,5-F3, 3-F,4-C 4-Cn' 4-F or 3-CN. The compound of formula I according to any one of claims 1 to 9, wherein R is fluorine and the value of the subscript η is 1. 11. A compound of formula I according to any one of claims 1 to 1 wherein r1 is ch2cn, ch2ch2f, CH2CHF2, CH2CF3, ch2och3 or CH2CsCH. 12. The compound of formula J according to any one of claims 1 to 11, wherein R1 is ch3. A method of preparing a compound of the formula I according to any one of claims 1 to 12, which is based on a Michael addition method to give a stupid acetonitrile derivative of the formula π 在鹼性條件下與式III之肉桂酸酯衍生物反應Reacts with the cinnamate derivative of formula III under basic conditions 14. 一種組合物，其包含除草有效量之至少一種如請求項！ 至12中任一項之式〗氰基丁酸化物化合物或其農業上適合 151170.doc 201127285 之鹽及慣用於調配作物保護劑之助劑。 15. —種控制不要之植被的方法，其包含使除草有效量之至 少一種如請求項1至12中任一項之式J氰基丁酸化物化合 物或其農業上合適之鹽作用於植物、其種子及/或其棲息 地。 151170.doc 201127285 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：14. A composition comprising at least one herbicidally effective amount as claimed; The cyanobutyrate compound of any of the formulas 12 or the agriculturally suitable salt of 151170.doc 201127285 and an adjuvant conventionally used for formulating crop protection agents. 15. A method of controlling unwanted vegetation, comprising causing at least one herbicidally effective amount of a cyanobutyrate compound of formula J according to any one of claims 1 to 12 or an agriculturally suitable salt thereof to act on a plant, Its seeds and / or its habitat. 151170.doc 201127285 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 151170.doc151170.doc
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