TW202044997A - Herbicidal compounds - Google Patents
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract
Description
本發明關於具有除草活性之嗒𠯤衍生物，並且關於用於製備此類衍生物之方法及中間體。本發明進一步延伸到包含此類衍生物之除草組成物，並且延伸到此類化合物和組成物在有用植物的作物中用於控制不希望的植物生長之用途，特別是用於控制雜草之用途。The present invention relates to a derivative of scalp with herbicidal activity, and also relates to methods and intermediates for preparing such derivatives. The present invention further extends to herbicidal compositions containing such derivatives, and to the use of such compounds and compositions in crops of useful plants for controlling undesirable plant growth, especially for controlling weeds .
無no
本發明基於以下發現：如在本文所定義的具有式 (I) 之嗒𠯤衍生物展示了出人意料地良好的除草活性。因此，根據本發明，提供了一種具有式 (I) 之化合物或其農學上可接受的鹽或兩性離子物種：
根據本發明的第二方面，提供了一種農業化學組成物，其包含除草有效量的具有式 (I) 之化合物和農用化學上可接受的稀釋劑或載體。這樣一種農業組成物可以進一步包含至少一種另外的活性成分。According to the second aspect of the present invention, an agrochemical composition is provided, which comprises a herbicidal effective amount of a compound of formula (I) and an agrochemically acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingredient.
根據本發明的第三方面，提供了一種控制或防止不希望的植物生長的方法，其中將除草有效量的具有式 (I) 之化合物或包含這種化合物作為活性成分的組成物施用至該植物、其部分或其所在場所。According to the third aspect of the present invention, there is provided a method for controlling or preventing the growth of undesirable plants, wherein a herbicidal effective amount of a compound having formula (I) or a composition containing this compound as an active ingredient is applied to the plant , Its part or its location.
根據本發明的第四方面，提供了具有式 (I) 之化合物作為除草劑之用途。According to the fourth aspect of the present invention, there is provided the use of the compound of formula (I) as a herbicide.
根據本發明的第五方面，提供了一種用於製備具有式 (I) 之化合物的方法。According to the fifth aspect of the present invention, there is provided a method for preparing a compound of formula (I).
如本文使用的，術語「鹵素（halogen或halo）」係指氟（fluorine，fluoro）、氯（chlorine，chloro）、溴（bromine，bromo）或碘（iodine，iodo），較佳的是氟、氯或溴。As used herein, the term "halogen (halogen or halo)" refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromo) or iodine (iodine, iodo), preferably fluorine, Chlorine or bromine.
如本文使用的，氰基意指-CN基團。As used herein, cyano means a -CN group.
如本文使用的，羥基意指-OH基團。As used herein, hydroxy means an -OH group.
如本文使用的，硝基意指-NO2 基團。As used herein, nitro means a -NO 2 group.
如本文使用的，術語「C1 -C6 烷基」係指僅由碳原子和氫原子組成的直鏈的或支鏈的烴鏈基團，該烴鏈基團不含不飽和度、具有從一至六個碳原子、並且藉由單鍵附接至分子的剩餘部分。C1 -C4 烷基和C1 -C2 烷基應相應地解釋。C1 -C6 烷基的實例包括但不限於甲基（Me）、乙基（Et）、正丙基、1-甲基乙基（異丙基）、正丁基和1-二甲基乙基（三級丁基）。As used herein, the term "C 1 -C 6 alkyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon atoms and hydrogen atoms. The hydrocarbon chain group does not contain unsaturation and has From one to six carbon atoms and attached to the rest of the molecule by a single bond. C 1 -C 4 alkyl and C 1 -C 2 alkyl should be interpreted accordingly. Examples of C 1 -C 6 alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethyl Ethyl (tertiary butyl).
如本文使用的，術語「C1 -C6 烷氧基」係指具有式-ORa 的基團，其中Ra 係如上一般定義的C1- C6 烷基基團。C1 -C4 烷氧基應相應地解釋。C1-4 烷氧基的實例包括但不限於甲氧基、乙氧基、丙氧基、異丙氧基和三級丁氧基。As used herein, the term "C 1 -C 6 alkoxy group" means a group having the formula -OR a, wherein R a line defined generally above C 1- C 6 alkyl group. C 1 -C 4 alkoxy should be interpreted accordingly. Examples of C 1-4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tertiary butoxy.
如本文使用的，術語「C1 -C6 鹵代烷基」係指如上一般定義的C1 -C6 烷基基團，其被一個或多個相同或不同的鹵素原子取代。C1 -C4 鹵代烷基應相應地解釋。C1 -C6 鹵代烷基的實例包括但不限於氯甲基、氟甲基、氟乙基、二氟甲基、三氟甲基和2,2,2-三氟乙基。As used herein, the term "C 1 -C 6 haloalkyl" refers to a C 1 -C 6 alkyl group as generally defined above, which is substituted by one or more identical or different halogen atoms. C 1 -C 4 haloalkyl should be interpreted accordingly. Examples of C 1 -C 6 haloalkyl groups include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.
如本文使用的，術語「C2 -C6 烯基」係指僅由碳原子和氫原子組成的直鏈或支鏈的烴鏈基團，該烴鏈基團含有至少一個可以是 (E )- 或 (Z )-組態的雙鍵，具有從二至六個碳原子，藉由單鍵附接至分子的剩餘部分。C2 -C4 烯基應相應地解釋。C2- C6 烯基的實例包括但不限於丙-1-烯基、烯丙基（丙-2-烯基）和丁-1-烯基。As used herein, the term "C 2 -C 6 alkenyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon atoms and hydrogen atoms, and the hydrocarbon chain group contains at least one ( E ) -Or ( Z )-configuration of double bonds, with from two to six carbon atoms, attached to the rest of the molecule by a single bond. C 2 -C 4 alkenyl should be interpreted accordingly. Examples of C 2- C 6 alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.
如本文使用的，術語「C2 -C6 鹵代烯基」係指被一個或多個相同的或不同的鹵素原子取代的如上一般定義的C2- C6 烯基基團。C2 -C6 鹵代烯基的實例包括但不限於氯乙烯、氟乙烯、1,1-二氟乙烯、1,1-二氯乙烯和1,1,2-三氯乙烯。As used herein, the term "C 2 -C 6 haloalkenyl group" means substituted by one or more identical or different halogen atoms as defined generally C 2- C 6 alkenyl group. Examples of C 2 -C 6 haloalkenyl groups include, but are not limited to, vinyl chloride, vinyl fluoride, 1,1-difluoroethylene, 1,1-dichloroethylene, and 1,1,2-trichloroethylene.
如本文中所使用的，術語「C2 -C6 炔基」係指僅由碳原子和氫原子組成的直鏈或支鏈的烴鏈基團，該烴鏈基團包含至少一個三鍵，具有從二至六個碳原子，並且其藉由單鍵附接至分子的剩餘部分。C2 -C4 炔基應相應地解釋。C2 -C6 炔基的實例包括但不限於丙-1-炔基、炔丙基（丙-2-炔基）和丁-1-炔基。As used herein, the term "C 2 -C 6 alkynyl" refers to a straight or branched hydrocarbon chain group consisting only of carbon atoms and hydrogen atoms, the hydrocarbon chain group containing at least one triple bond, It has from two to six carbon atoms, and it is attached to the rest of the molecule by a single bond. The C 2 -C 4 alkynyl group should be interpreted accordingly. Examples of C 2 -C 6 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.
如本文使用的，術語「C1 -C6 鹵代烷氧基」係指如上所定義的C1 -C6 烷氧基基團，其被一個或多個相同或不同的鹵素原子取代。C1 -C4 鹵代烷氧基應相應地解釋。C1 -C6 鹵代烷氧基的實例包括但不限於氟甲氧基、二氟甲氧基、氟乙氧基、三氟甲氧基和三氟乙氧基。As used herein, the term "C 1 -C 6 haloalkoxy" refers to a C 1 -C 6 alkoxy group as defined above, which is substituted by one or more identical or different halogen atoms. C 1 -C 4 haloalkoxy should be interpreted accordingly. Examples of C 1 -C 6 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.
如本文使用的，術語「C1 -C3 鹵代烷氧基C1 -C3 烷基」係指具有式Rb -O-Ra -的基團，其中Rb 係如上一般定義的C1 -C3 鹵代烷基基團，並且Ra 係如上一般定義的C1 -C3 伸烷基基團。As used herein, the term "C 1 -C 3 haloalkoxy C 1 -C 3 alkyl" refers to a group having the formula R b -OR a -, where R b is C 1 -C 3 as generally defined above A halogenated alkyl group, and Ra is a C 1 -C 3 alkylene group as generally defined above.
如本文使用的，術語「C1 -C3 烷氧基C1 -C3 烷基」係指具有式Rb -O-Ra -的基團，其中Rb 係如上一般定義的C1 -C3 烷基基團，並且Ra 係如上一般定義的C1 -C3 伸烷基基團。As used herein, the term "C 1 -C 3 alkoxy C 1 -C 3 alkyl" refers to a group having the formula R b -OR a -, where R b is C 1 -C 3 as generally defined above An alkyl group, and Ra is a C 1 -C 3 alkylene group as generally defined above.
如本文使用的，術語「C1 -C3 烷氧基C1 -C3 烷氧基」係指具有式Rb -O-Ra -O-的基團，其中Rb 係如上一般定義的C1 -C3 烷基基團，並且Ra 係如上一般定義的C1 -C3 伸烷基基團。As used herein, the term "C 1 -C 3 alkoxy C 1 -C 3 alkoxy" refers to a group having the formula R b -OR a -O-, where R b is C 1 as generally defined above -C 3 alkyl group, and Ra is a C 1 -C 3 alkylene group as generally defined above.
如本文使用的，術語「C3 -C6 烯基氧基」係指具有式-ORa 的基團，其中Ra 係如上一般定義的C3- C6 烯基基團。As used herein, the term "C 3 -C 6 alkenyloxy" refers to a group having the formula -OR a , where Ra is a C 3 -C 6 alkenyl group as generally defined above.
如本文使用的，術語「C3 -C6 炔基氧基」係指具有式-ORa 的基團，其中Ra 係如上一般定義的C3- C6 炔基基團。As used herein, the term "C 3 -C 6 alkynyloxy" refers to a group having the formula -OR a , where Ra is a C 3 -C 6 alkynyl group as generally defined above.
如本文使用的，術語「羥基C1 -C6 烷基」係指被一個或多個羥基基團取代的如上一般定義的C1 -C6 烷基基團。As used herein, the term "hydroxy C 1 -C 6 alkyl" refers to a C 1 -C 6 alkyl group as generally defined above, substituted with one or more hydroxyl groups.
如本文使用的，術語「C1 -C6 烷基羰基」係指具有式-C(O)Ra 的基團，其中Ra 係如上一般定義的C1 -C6 烷基基團。As used herein, the term "C 1 -C 6 alkylcarbonyl group" means a group having the formula -C (O) R a, wherein R a line generally defined as C 1 -C 6 alkyl group.
如本文使用的，術語「C1 -C6 烷氧基羰基」係指具有式-C(O)ORa 的基團，其中Ra 係如上一般定義的C1 -C6 烷基基團。As used herein, the term "C 1 -C 6 alkoxycarbonyl" refers to a group having the formula -C(O)OR a , where Ra is a C 1 -C 6 alkyl group as generally defined above.
如本文使用的，術語「胺基羰基」係指具有式-C(O)NH2 的基團。As used herein, the term "aminocarbonyl" means (O) NH group of formula -C 2.
如本文使用的，術語「C3 -C6 環烷基」係指飽和或部分不飽和並且含有3至6個碳原子的穩定的單環基團。C3 -C4 環烷基應相應地解釋。C3 -C6 環烷基的實例包括但不限於環丙基、環丁基、環戊基和環己基。As used herein, the term "C 3 -C 6 cycloalkyl" refers to a stable monocyclic group that is saturated or partially unsaturated and contains 3 to 6 carbon atoms. The C 3 -C 4 cycloalkyl should be interpreted accordingly. Examples of C 3 -C 6 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
如本文使用的，術語「C3 -C6 鹵代環烷基」係指被一個或多個相同的或不同的鹵素原子取代的如上一般定義的C3 -C6 環烷基基團。C3 -C4 鹵代環烷基應相應地解釋。As used herein, the term "C 3 -C 6 halocycloalkyl" refers to a C 3 -C 6 cycloalkyl group as generally defined above substituted by one or more identical or different halogen atoms. The C 3 -C 4 halocycloalkyl should be interpreted accordingly.
如本文使用的，術語「C3 -C6 環烷氧基」係指具有式-ORa 的基團，其中Ra 係如上一般定義的C3 -C6 環烷基基團。As used herein, the term "C 3 -C 6 cycloalkoxy" refers to a group having the formula -OR a , where Ra is a C 3 -C 6 cycloalkyl group as generally defined above.
如本文使用的，術語「N-C3- C6 環烷基胺基」係指具有式-NHRa 的基團，其中Ra 係如上一般定義的C3- C6 環烷基基團。As used herein, the term "NC 3- C 6 cycloalkylamino" refers to a group having the formula -NHR a , where Ra is a C 3 -C 6 cycloalkyl group as generally defined above.
如本文使用的，除非另外明確說明，術語「雜芳基」係指包含1、2、3或4個單獨地選自氮、氧和硫的雜原子的5員或6員單環芳族環。該雜芳基基團可以經碳原子或雜原子鍵合至分子的剩餘部分。雜芳基的實例包括呋喃基、吡咯基、咪唑基、噻吩基、吡唑基、噻唑基、異噻唑基、㗁唑基、異㗁唑基、三唑基、四唑基、吡𠯤基、嗒𠯤基、嘧啶基或吡啶基。As used herein, unless expressly stated otherwise, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur . The heteroaryl group may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heteroaryl groups include furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, azazolyl, isozolyl, triazolyl, tetrazolyl, pyrazolyl, Da𠯤yl, pyrimidinyl or pyridyl.
如本文使用的，除非另外明確說明，術語「雜環基」或「雜環的」係指包含1、2或3個單獨地選自氮、氧和硫的雜原子的穩定的4員至6員非芳族單環基團。該雜環基基團可以經由碳原子或雜原子鍵合至分子的剩餘部分。雜環基的實例包括但不限於吡咯啉基、吡咯啶基、四氫呋喃基、四氫噻吩基、四氫噻喃基、哌啶基、哌𠯤基、四氫哌喃基、二氫異㗁唑基、二氧戊環基、𠰌啉基或δ-內醯胺基（lactamyl）。As used herein, unless expressly stated otherwise, the term "heterocyclyl" or "heterocyclic" refers to a stable 4 to 6 member containing 1, 2, or 3 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Member is a non-aromatic monocyclic group. The heterocyclyl group may be bonded to the rest of the molecule via a carbon atom or a heteroatom. Examples of heterocyclic groups include, but are not limited to, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperidine, tetrahydropiperanyl, dihydroisoxazole Group, dioxolane group, 𠰌line group or delta-lactamyl group (lactamyl).
在具有式 (I) 之化合物中一個或多個可能的不對稱碳原子的存在意味著該化合物能以手性異構物形式存在，即鏡像異構物或非鏡像異構物的形式。作為圍繞單鍵的受限旋轉的結果，還可能存在阻轉異構物。式 (I) 旨在包括所有那些可能的異構形式以及其混合物。本發明包括具有式 (I) 之化合物的所有那些可能的異構物形式及其混合物。同樣地，式 (I) 旨在包括所有可能的互變異構物（包括內醯胺-內醯亞胺互變異構和酮-烯醇互變異構）（當存在時）。本發明包括具有式 (I) 之化合物的所有可能的互變異構形式。類似地，在存在雙取代烯烴的情況下，該等能以E 或Z 形式或作為任何比例的二者的混合物而存在。本發明包括具有式 (I) 之化合物的所有該等可能的異構物形式及其混合物。The presence of one or more possible asymmetric carbon atoms in the compound of formula (I) means that the compound can exist in the form of chiral isomers, that is, in the form of enantiomers or diastereomers. As a result of restricted rotation around a single bond, atropisomers may also exist. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms of the compound of formula (I) and mixtures thereof. Likewise, formula (I) is intended to include all possible tautomers (including lactam-endoimine tautomerism and keto-enol tautomerism) (when present). The present invention includes all possible tautomeric forms of compounds of formula (I). Similarly, in the presence of disubstituted olefins, these can exist in E or Z form or as a mixture of the two in any ratio. The present invention includes all such possible isomeric forms of the compound of formula (I) and mixtures thereof.
具有式 (I) 之化合物將通常以農學上可接受的鹽、兩性離子或農學上可接受的兩性離子鹽的形式提供。本發明涵蓋所有比例的所有此類農學上可接受的鹽、兩性離子及其混合物。The compound of formula (I) will usually be provided in the form of an agronomically acceptable salt, a zwitterionic or agronomically acceptable zwitterionic salt. The present invention encompasses all such agronomically acceptable salts, zwitterions and mixtures thereof in all proportions.
例如，具有式 (I) 之化合物（其中Z包含酸性質子）可以作為以下存在：兩性離子，即具有式 (I-I) 之化合物，或農學上可接受的鹽，即具有式 (I-II) 之化合物，如下所示：
具有式 (I) 之化合物也可以作為農學上可接受的兩性離子鹽存在，即具有式 (I-III) 之化合物，如下所示：
因此，當本文中以質子化形式繪製具有式 (I) 之化合物時，技術人員將理解，它同樣可以用一種或多種相關相對離子以未質子化或鹽形式表示。Therefore, when the compound of formula (I) is drawn in protonated form herein, the skilled person will understand that it can also be represented in unprotonated or salt form with one or more related relative ions.
在本發明的一個實施方式中，提供了具有式 (I-II) 之化合物，其中k為2，j為1且Y選自由以下項組成之群組：鹵素、三氟乙酸鹽和五氟丙酸鹽。在此實施方式中，環A中的氮原子可以被質子化或者R1 、R2 、R8 、Q或X中包含的氮原子可以被質子化。較佳的是，在具有式 (I-II) 之化合物中，k為2，j為1且Y為氯，其中環A中的氮原子被質子化。In one embodiment of the present invention, a compound having formula (I-II) is provided, wherein k is 2, j is 1, and Y is selected from the group consisting of halogen, trifluoroacetate and pentafluoropropane Acid salt. In this embodiment, the nitrogen atom in the ring A may be protonated or the nitrogen atom contained in R 1 , R 2 , R 8 , Q or X may be protonated. Preferably, in the compound of formula (I-II), k is 2, j is 1 and Y is chlorine, wherein the nitrogen atom in ring A is protonated.
本發明的合適的農學上可接受的鹽（由陰離子Y表示）包括但不限於氯化物、溴化物、碘化物、氟化物、2-萘磺酸鹽、乙酸鹽、己二酸鹽、甲醇鹽、乙醇鹽、丙醇鹽、丁醇鹽、天冬胺酸鹽、苯磺酸鹽、苯甲酸鹽、碳酸氫鹽、硫酸氫鹽、酒石酸氫鹽、丁基硫酸鹽、丁基磺酸鹽、丁酸鹽、樟腦酸鹽、樟腦磺酸鹽（camsylate）、癸酸鹽、己酸鹽、辛酸鹽、碳酸鹽、檸檬酸鹽、二磷酸鹽、依地酸鹽、乙二磺酸鹽、庚酸鹽、乙二磺酸鹽、乙磺酸鹽、乙基硫酸鹽、甲酸鹽、富馬酸鹽、葡庚糖酸鹽、葡糖酸鹽、葡糖醛酸鹽、麩胺酸鹽、甘油磷酸鹽、十七烷酸鹽、十六烷酸鹽、硫酸氫鹽、氫氧化物、羥萘甲酸鹽、羥乙磺酸鹽、乳酸鹽、乳糖酸鹽、月桂酸鹽、蘋果酸鹽、馬來酸鹽、苦杏仁酸鹽、甲磺酸鹽、甲二磺酸鹽、甲基硫酸鹽、黏酸鹽、肉豆蔻酸鹽、萘磺酸鹽、硝酸鹽、十九烷酸鹽、十八烷酸鹽、草酸鹽、壬酸鹽、十五烷酸鹽、五氟丙酸鹽、過氯酸鹽、磷酸鹽、丙酸鹽、丙基硫酸鹽、丙磺酸鹽、琥珀酸鹽、硫酸鹽、酒石酸鹽、甲苯磺酸鹽、十三烷酸鹽（tridecylate）、三氟甲磺酸鹽、三氟乙酸鹽、十一烷酸鹽（undecylinate）和戊酸鹽。Suitable agronomically acceptable salts of the present invention (represented by the anion Y) include but are not limited to chloride, bromide, iodide, fluoride, 2-naphthalenesulfonate, acetate, adipate, methoxide , Ethoxide, propoxide, butoxide, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, butyl sulfate, butanesulfonate , Butyrate, camphorate, camphor sulfonate (camsylate), caprate, caproate, caprylate, carbonate, citrate, diphosphate, edetate, ethanedisulfonate, Enanthate, ethanedisulfonate, ethanesulfonate, ethyl sulfate, formate, fumarate, glucoheptonate, gluconate, glucuronate, glutamate , Glyceryl phosphate, heptadecanoate, palmitate, bisulfate, hydroxide, hydroxynaphthoate, isethionate, lactate, lactobionate, laurate, malic acid Salt, maleate, mandelic acid, methanesulfonate, methanesulfonate, methylsulfate, mucate, myristate, naphthalenesulfonate, nitrate, nonadecanate , Octadecanoate, oxalate, nonanoate, pentadecanoate, pentafluoropropionate, perchlorate, phosphate, propionate, propyl sulfate, propanesulfonate, succinate Acid salt, sulfate, tartrate, tosylate, tridecylate, triflate, trifluoroacetate, undecylinate, and valerate.
由M表示的合適的陽離子包括但不限於金屬、胺的共軛酸和有機陽離子。合適的金屬的實例包括鋁、鈣、銫、銅、鋰、鎂、錳、鉀、鈉、鐵和鋅。合適的胺的實例包括烯丙胺、氨、戊胺、精胺酸、苯乙苄胺、苄星青黴素（benzathine）、丁烯基-2-胺、丁胺、丁基乙醇胺、環己胺、癸胺、二戊胺、二丁胺、二乙醇胺、二乙胺、二乙三胺、二庚胺、二己胺、二異戊胺、二異丙胺、二甲胺、二辛胺、二丙醇胺、二炔丙胺、二丙胺、十二胺、乙醇胺、乙胺、乙基丁胺、乙二胺、乙基庚胺、乙基辛胺、乙基丙醇胺、十七胺、庚胺、十六胺、己烯基-2-胺、己胺、己基庚胺、己基辛胺、組胺酸、吲哚啉、異戊胺、異丁醇胺、異丁胺、異丙醇胺、異丙胺、離胺酸、葡甲胺、甲氧基乙胺、甲胺、甲基丁胺、甲基乙胺、甲基己胺、甲基異丙胺、甲基壬胺、甲基十八胺、甲基十五胺、𠰌啉、N,N-二乙基乙醇胺、N-甲基哌𠯤、壬胺、十八胺、辛胺、油胺、十五胺、戊烯基-2-胺、苯氧基乙胺、甲基吡啶、哌𠯤、哌啶、丙醇胺、丙胺、丙二胺、吡啶、吡咯啶、二級丁胺、硬脂醯胺、牛脂胺、十四胺、三丁胺、十三胺、三甲胺、三庚胺、三己胺、三異丁胺、三異癸胺、三異丙胺、三甲胺、三戊胺、三丙胺、三(羥甲基)胺基甲烷和十一胺。合適的有機陽離子的實例包括苄基三丁基銨、苄基三甲基銨、苄基三苯基鏻、膽鹼、四丁基銨、四丁基鏻、四乙基銨、四乙基鏻、四甲基銨、四甲基鏻、四丙基銨、四丙基鏻、三丁基鋶、三丁基氧化鋶、三乙基鋶、三乙基氧化鋶、三甲基鋶、三甲基氧化鋶、三丙基鋶和三丙基氧化鋶。Suitable cations represented by M include, but are not limited to, conjugate acids of metals, amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc. Examples of suitable amines include allylamine, ammonia, amylamine, arginine, phenethylbenzylamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine Amine, dipentylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisopentylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanol Amine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecamine, heptylamine, Cetylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, iso Propylamine, lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, Methylpentadecylamine, pentadecylamine, N,N-diethylethanolamine, N-methylpiperamine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, Phenoxyethylamine, picoline, piperidine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, secondary butylamine, stearylamine, tallow amine, tetradecylamine, tributyl Amine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane And undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium , Tetramethyl ammonium, tetramethyl phosphonium, tetrapropyl ammonium, tetrapropyl phosphonium, tributyl sulfonium, tributyl sulfonium oxide, triethyl sulfonium, triethyl sulfonium oxide, trimethyl sulfonium, trimethyl Base sulfonium oxide, tripropyl sulfonium oxide and tripropyl sulfonium oxide.
較佳的其中Z包含酸性質子的具有式 (I) 之化合物可以表示為 (I-I) 或 (I-II)。對於具有式 (I-II) 之化合物，當Y係氯化物、溴化物、碘化物、氫氧化物、碳酸氫鹽、乙酸鹽、五氟丙酸鹽、三氟甲磺酸鹽、三氟乙酸鹽、甲基硫酸鹽、甲苯磺酸鹽和硝酸鹽（其中j和k係1）時，強調了鹽。較佳的是，Y係氯化物、溴化物、碘化物、氫氧化物、碳酸氫鹽、乙酸鹽、三氟乙酸鹽、甲基硫酸鹽、甲苯磺酸鹽和硝酸鹽，其中j和k係1。對於具有式 (I-II) 之化合物，重點還是當Y係碳酸根和硫酸根（其中j為2且k為1）時和當Y係磷酸根（其中j為3且k為1）時的鹽。Preferred compounds of formula (I) in which Z contains an acidic proton can be represented by (I-I) or (I-II). For compounds of formula (I-II), when Y series chloride, bromide, iodide, hydroxide, bicarbonate, acetate, pentafluoropropionate, trifluoromethanesulfonate, trifluoroacetic acid When salt, methyl sulfate, tosylate and nitrate (where j and k are 1), the salt is emphasized. Preferably, Y series chloride, bromide, iodide, hydroxide, bicarbonate, acetate, trifluoroacetate, methyl sulfate, tosylate and nitrate, wherein j and k are 1. For compounds of formula (I-II), the focus is still on when Y is carbonate and sulfate (where j is 2 and k is 1) and when Y is phosphate (where j is 3 and k is 1) salt.
適當時，具有式 (I) 之化合物也可以處於N-氧化物的形式（和/或用作N-氧化物）。Where appropriate, the compound of formula (I) may also be in the form of an N-oxide (and/or be used as an N-oxide).
其中m為0且n為0的具有式 (I) 之化合物可以由具有式 (I-Ia) 之化合物表示，如下所示：
其中m為1且n為0的具有式 (I) 之化合物可以由具有式 (I-Ib) 之化合物表示，如下所示：
其中m為2且n為0的具有式 (I) 之化合物可以由具有式 (I-Ic) 之化合物表示，如下所示：
其中m為3且n為0的具有式 (I) 之化合物可以由具有式 (I-Id) 之化合物表示，如下所示：
以下清單提供了關於根據本發明的具有式 (I) 之化合物的取代基n、m、p、r、Q、X、Z、R1 、R2 、R1a 、R2b 、R3 、R4 、R5 、R6 、R7 、R7a 、R7b 、R7c 、R8 、R9 、R10 、R11 、R12 、R13 、R14 、R15 、R15a 、R16 、R17 和R18 的定義，包括較佳的定義。對於該等取代基中的任何一個，以下給出的任何定義都可以結合以下或在本文件中的其他地方給出的任何其他取代基的任何定義。The following list provides the substituents n, m, p, r, Q, X, Z, R 1 , R 2 , R 1a , R 2b , R 3 , R 4 for the compounds of formula (I) according to the present invention , R 5 , R 6 , R 7 , R 7a , R 7b , R 7c , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 15a , R 16 , R The definitions of 17 and R 18 include preferred definitions. For any of these substituents, any definition given below can be combined with any definition of any other substituent given below or elsewhere in this document.
R1 選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基、C2 -C6 烯基、C2 -C6 炔基、C3 -C6 環烷基、C1 -C6 鹵代烷基、-OR7 、-OR15a 、-N(R6 )S(O)2 R15 、-N(R6 )C(O)R15 、-N(R6 )C(O)OR15 、-N(R6 )C(O)NR16 R17 、-N(R6 )CHO、-N(R7a )2 和-S(O)r R15 。較佳的是，R1 選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基、C1 -C6 氟烷基、-OR7 、-NHS(O)2 R15 、-NHC(O)R15 、-NHC(O)OR15 、-NHC(O)NR16 R17 、-N(R7a )2 和-S(O)r R15 。更較佳的是，R1 選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基、C1 -C6 氟烷基、-OR7 和-N(R7a )2 。甚至更較佳的是，R1 選自由以下項組成之群組：氫、C1 -C6 烷基、-OR7 和-N(R7a )2 。甚至還更較佳的是，R1 係氫或C1 -C6 烷基。又甚至還更較佳的是，R1 係氫或甲基。最較佳的是，R1 係氫。R 1 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, -OR 7 , -OR 15a , -N(R 6 )S(O) 2 R 15 , -N(R 6 )C(O)R 15 , -N(R 6 )C(O )OR 15 , -N(R 6 )C(O)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(O) r R 15 . Preferably, R 1 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, -OR 7 , -NHS(O) 2 R 15 , -NHC(O)R 15 , -NHC(O)OR 15 , -NHC(O)NR 16 R 17 , -N(R 7a ) 2 and -S(O) r R 15 . More preferably, R 1 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, -OR 7 and -N(R 7a ) 2 . Even more preferably, R 1 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, -OR 7 and -N(R 7a ) 2 . Even more preferably, R 1 is hydrogen or C 1 -C 6 alkyl. Even more preferably, R 1 is hydrogen or methyl. Most preferably, R 1 is hydrogen.
R2 選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基和C1 -C6 鹵代烷基。較佳的是，R2 選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基和C1 -C6 氟烷基。更較佳的是，R2 係氫或C1 -C6 烷基。甚至更較佳的是，R2 係氫或甲基。最較佳的是，R2 係氫。R 2 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl and C 1 -C 6 haloalkyl. Preferably, R 2 is selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl and C 1 -C 6 fluoroalkyl. More preferably, R 2 is hydrogen or C 1 -C 6 alkyl. Even more preferably, R 2 is hydrogen or methyl. Most preferably, R 2 is hydrogen.
其中當R1 選自由-OR7 、-OR15a 、-N(R6 )S(O)2 R15 、-N(R6 )C(O)R15 、-N(R6 )C(O)OR15 、-N(R6 )C(O)NR16 R17 、-N(R6 )CHO、-N(R7a )2 和-S(O)r R15 組成之群組時，R2 選自由以下項組成之群組：氫和C1 -C6 烷基。較佳的是，當R1 選自由-OR7 、-NHS(O)2 R15 、-NHC(O)R15 、-NHC(O)OR15 、-NHC(O)NR16 R17 、-N(R7a )2 和-S(O)r R15 組成之群組時，R2 選自由以下項組成之群組：氫和甲基。Where R 1 is selected from -OR 7 , -OR 15a , -N(R 6 )S(O) 2 R 15 , -N(R 6 )C(O)R 15 , -N(R 6 )C(O )OR 15 , -N(R 6 )C(O)NR 16 R 17 , -N(R 6 )CHO, -N(R 7a ) 2 and -S(O) r R 15 when the group is formed, R 2 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Preferably, when R 1 is selected from -OR 7 , -NHS(O) 2 R 15 , -NHC(O)R 15 , -NHC(O)OR 15 , -NHC(O)NR 16 R 17 ,- When N(R 7a ) 2 and -S(O) r R 15 are in the group, R 2 is selected from the group consisting of hydrogen and methyl.
可替代地，R1 和R2 與它們所附接的碳原子一起形成C3 -C6 環烷基環或3員至6員雜環基，該雜環基包含1或2個單獨地選自N和O的雜原子。較佳的是，R1 和R2 與它們所附接的碳原子一起形成C3 -C6 環烷基環。更較佳的是，R1 和R2 與它們所附接的碳原子一起形成環丙基環。Alternatively, R 1 and R 2 together with the carbon atoms to which they are attached form a C 3 -C 6 cycloalkyl ring or a 3- to 6-membered heterocyclic group, the heterocyclic group comprising 1 or 2 independently selected Heteroatoms from N and O. Preferably, R 1 and R 2 together with the carbon atom to which they are attached form a C 3 -C 6 cycloalkyl ring. More preferably, R 1 and R 2 form a cyclopropyl ring together with the carbon atom to which they are attached.
在一個實施方式中，R1 和R2 係氫。In one embodiment, R 1 and R 2 are hydrogen.
在另一個實施方式中，R1 係甲基並且R2 係氫。In another embodiment, R 1 is methyl and R 2 is hydrogen.
在另一個實施方式中，R1 係甲基並且R2 係甲基。In another embodiment, R 1 is a methyl group and R 2 is a methyl group.
Q係(CR1a R2b )m 。Q series (CR 1a R 2b ) m .
m係0、1、2或3。較佳的是，m係0、1或2。更較佳的是，m係1或2。最較佳的是，m係1。m is 0, 1, 2 or 3. Preferably, m is 0, 1, or 2. More preferably, m is 1 or 2. Most preferably, m is 1.
每個R1a 和R2b 獨立地選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基、C1 -C6 鹵代烷基、-OH、-OR7 、-OR15a 、-NH2 、-NHR7 、-NHR15a 、-N(R6 )CHO、-NR7b R7c 以及-S(O)r R15 。較佳的是，每個R1a 和R2b 獨立地選自由以下項組成之群組：氫、鹵素、C1 -C6 烷基、C1 -C6 氟烷基、-OH、-NH2 和-NHR7 。更較佳的是，每個R1a 和R2b 獨立地選自由以下項組成之群組：氫、C1 -C6 烷基、-OH和-NH2 。甚至更較佳的是，每個R1a 和R2b 獨立地選自由以下項組成之群組：氫、甲基、-OH和-NH2 。甚至還更較佳的是，每個R1a 和R2b 獨立地選自由以下項組成之群組：氫和甲基。最較佳的是，R1a 和R2b 係氫。Each of R 1a and R 2b is independently selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, -OH, -OR 7 , -OR 15a ,- NH 2 , -NHR 7 , -NHR 15a , -N(R 6 )CHO, -NR 7b R 7c, and -S(O) r R 15 . Preferably, each of R 1a and R 2b is independently selected from the group consisting of hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, -OH, -NH 2 And -NHR 7 . More preferably, each of R 1a and R 2b is independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, -OH and -NH 2 . Even more preferably, each of R 1a and R 2b is independently selected from the group consisting of hydrogen, methyl, -OH, and -NH 2 . Even more preferably, each of R 1a and R 2b is independently selected from the group consisting of hydrogen and methyl. Most preferably, R 1a and R 2b are hydrogen.
在另一個實施方式中，每個R1a 和R2b 獨立地選自由以下項組成之群組：氫和C1 -C6 烷基。In another embodiment, each of R 1a and R 2b is independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl.
可替代地，每個R1a 和R2b 與它們所附接的碳原子一起形成C3 -C6 環烷基環或3員至6員雜環基，該雜環基包含1或2個單獨地選自N和O的雜原子。較佳的是，每個R1a 和R2b 與它們所附接的碳原子一起形成C3 -C6 環烷基環。更較佳的是，每個R1a 和R2b 與它們所附接的碳原子一起形成環丙基環。Alternatively, each of R 1a and R 2b together with the carbon atom to which they are attached forms a C 3 -C 6 cycloalkyl ring or a 3- to 6-membered heterocyclic group, which includes 1 or 2 separate Heteroatoms selected from N and O. Preferably, each of R 1a and R 2b together with the carbon atom to which they are attached forms a C 3 -C 6 cycloalkyl ring. More preferably, each of R 1a and R 2b together with the carbon atom to which they are attached forms a cyclopropyl ring.
R3 、R4 和R5 獨立地選自由以下項組成之群組：氫、鹵素、氰基、硝基、-S(O)r R15 、C1 -C6 烷基、C1 -C6 氟烷基、C1 -C6 氟烷氧基、C1 -C6 烷氧基、C3 -C6 環烷基以及-N(R6 )2 。較佳的是，R3 、R4 和R5 獨立地選自由以下項組成之群組：氫、C1 -C6 烷基、C1 -C6 氟烷基、C1 -C6 氟烷氧基、C1 -C6 烷氧基、C3 -C6 環烷基以及-N(R6 )2 。更較佳的是，R3 、R4 和R5 獨立地選自由以下項組成之群組：氫、C1 -C6 烷基和C1 -C6 烷氧基。甚至更較佳的是，R3 、R4 和R5 獨立地選自由以下項組成之群組：氫和C1 -C6 烷基。甚至還更較佳的是，R3 、R4 和R5 獨立地選自由以下項組成之群組：氫和甲基。最較佳的是，R3 、R4 和R5 係氫。R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, -S(O) r R 15 , C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, C 1 -C 6 fluoroalkoxy, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, and -N(R 6 ) 2 . Preferably, R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 fluoroalkyl, C 1 -C 6 fluoroalkane Oxy, C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, and -N(R 6 ) 2 . More preferably, R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy. Even more preferably, R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Even more preferably, R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen and methyl. Most preferably, R 3 , R 4 and R 5 are hydrogen.
每個R6 獨立地選自氫和C1 -C6 烷基。較佳的是，每個R6 獨立地選自氫和甲基。Each R 6 is independently selected from hydrogen and C 1 -C 6 alkyl. Preferably, each R 6 is independently selected from hydrogen and methyl.
每個R7 獨立地選自由以下項組成之群組：C1 -C6 烷基、-S(O)2 R15 、-C(O)R15 、-C(O)OR15 以及-C(O)NR16 R17 。較佳的是，每個R7 獨立地選自由以下項組成之群組：C1 -C6 烷基、-C(O)R15 和-C(O)NR16 R17 。更較佳的是，每個R7 係C1 -C6 烷基。最較佳的是，每個R7 係甲基。Each R 7 is independently selected from the group consisting of: C 1 -C 6 alkyl, -S(O) 2 R 15 , -C(O)R 15 , -C(O)OR 15 and -C (O)NR 16 R 17 . Preferably, each R 7 is independently selected from the group consisting of C 1 -C 6 alkyl, -C(O)R 15 and -C(O)NR 16 R 17 . More preferably, each R 7 is a C 1 -C 6 alkyl group. Most preferably, each R 7 is a methyl group.
每個R7a 獨立地選自由以下項組成之群組：-S(O)2 R15 、-C(O)R15 、-C(O)OR15 、-C(O)NR16 R17 和-C(O)NR6 R15a 。較佳的是，每個R7a 獨立地是-C(O)R15 或-C(O)NR16 R17 。Each R 7a is independently selected from the group consisting of: -S(O) 2 R 15 , -C(O)R 15 , -C(O)OR 15 , -C(O)NR 16 R 17 and -C(O)NR 6 R 15a . Preferably, each R 7a is independently -C(O)R 15 or -C(O)NR 16 R 17 .
R7b 和R7c 獨立地選自由以下項組成之群組：C1 -C6 烷基、-S(O)2 R15 、-C(O)R15 、-C(O)OR15 、-C(O)NR16 R17 和苯基，並且其中該苯基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R7b 和R7c 獨立地選自由以下項組成之群組：C1 -C6 烷基、-C(O)R15 和-C(O)NR16 R17 。更較佳的是，R7b 和R7c 係C1 -C6 烷基。最較佳的是，R7b 和R7c 係甲基。R 7b and R 7c are independently selected from the group consisting of: C 1 -C 6 alkyl, -S(O) 2 R 15 , -C(O)R 15 , -C(O)OR 15 ,- C(O)NR 16 R 17 and a phenyl group, and wherein the phenyl group is optionally substituted with 1, 2 or 3 R 9 substituents which may be the same or different. Preferably, R 7b and R 7c are independently selected from the group consisting of C 1 -C 6 alkyl, -C(O)R 15 and -C(O)NR 16 R 17 . More preferably, R 7b and R 7c are C 1 -C 6 alkyl groups. Most preferably, R 7b and R 7c are methyl groups.
可替代地，R7b 和R7c 與它們所附接的氮原子一起形成4員至6員雜環基環，該雜環基環視需要包含一個另外的單獨地選自N、O和S的雜原子。較佳的是，R7b 和R7c 與它們所附接的氮原子一起形成5員至6員雜環基環，該雜環基環視需要包含一個另外的單獨地選自N和O的雜原子。更較佳的是，R7b 和R7c 與它們所附接的氮原子一起形成吡咯啶基、㗁唑啶基、咪唑啶基、哌啶基、哌𠯤基或𠰌啉基基團。Alternatively, R 7b and R 7c together with the nitrogen atom to which they are attached form a 4-membered to 6-membered heterocyclyl ring, which optionally contains an additional heterocyclic ring independently selected from N, O and S atom. Preferably, R 7b and R 7c together with the nitrogen atom to which they are attached form a 5-membered to 6-membered heterocyclyl ring, and the heterocyclyl ring optionally contains an additional heteroatom independently selected from N and O . More preferably, R 7b and R 7c together with the nitrogen atom to which they are attached form a pyrrolidinyl, azolidine, imidazolidinyl, piperidinyl, piperidinyl, or pyrrolidinyl group.
較佳的是，A包含1、2、3或4個雜原子，更較佳的是1、2或3個雜原子，甚至更較佳的是1或2個雜原子，並且最較佳的是2個雜原子。較佳的是，A在環A1 或A2 中包含至少一個氮原子。Preferably, A contains 1, 2, 3 or 4 heteroatoms, more preferably 1, 2 or 3 heteroatoms, even more preferably 1 or 2 heteroatoms, and most preferably Are 2 heteroatoms. Preferably, A contains at least one nitrogen atom in ring A 1 or A 2 .
較佳的是，p係0、1或2，更較佳的是0或1，最較佳的是0。Preferably, p is 0, 1, or 2, more preferably 0 or 1, and most preferably 0.
A的代表性環結構為以下A-I至A-XXVIII。The representative ring structure of A is the following A-I to A-XXVIII.
在一組實施方式中，A的較佳的環結構係A-I、A-II、A-III、A-IV、A-V、A-VI、A-VII、A-VIII、A-IX、A-X、A-XI、A-XII和A-XIII。在這組實施方式中，A更較佳的環結構係AI、A-II、A-VI和A-XIII。In a set of embodiments, the preferred ring structure of A is AI, A-II, A-III, A-IV, AV, A-VI, A-VII, A-VIII, A-IX, AX, A -XI, A-XII and A-XIII. In this group of embodiments, the more preferred ring structures of A are AI, A-II, A-VI and A-XIII.
在另一組實施方式中，A的較佳的環結構係A-I、A-II、A-III、A-VI、A-XIII、A-XIV、A-XV、A-XVI、A-XVII、A-XVIII、A-XIX、A-XX、A-XXI、A-XXII、A-XXIII、A-XXIV、A-XXV、A-XXVI、A-XXVII和A-XXVIII。
較佳的是，當R8 附接至C時，它獨立地選自：氯、氟、氰基、-NH2 、-N(Me)2 、-OH、-OMe、-S(O)2 Me、-C(O)OMe、-C(O)OH、-C(O)Me、-C(O)NH2 、-C(O)NHMe、-C(O)N(Me)2 、甲基、乙基以及三氟甲基，更較佳的是甲基或NH2 ，還更較佳的是甲基。較佳的是，當R8 附接至N時，它獨立地選自氫、甲基和乙基，更較佳的是甲基。Preferably, when R 8 is attached to C, it is independently selected from: chlorine, fluorine, cyano, -NH 2 , -N(Me) 2 , -OH, -OMe, -S(O) 2 Me, -C(O)OMe, -C(O)OH, -C(O)Me, -C(O)NH 2 , -C(O)NHMe, -C(O)N(Me) 2 , A Group, ethyl and trifluoromethyl, more preferably methyl or NH 2 , still more preferably methyl. Preferably, when R 8 is attached to N, it is independently selected from hydrogen, methyl and ethyl, more preferably methyl.
較佳的是，每個R9 獨立地選自由以下項組成之群組：鹵素、氰基、-N(R6 )2 、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 鹵代烷基和C1 -C4 鹵代烷氧基。更較佳的是，每個R9 獨立地選自由以下項組成之群組：鹵素、C1 -C4 烷基、C1 -C4 烷氧基和C1 -C4 鹵代烷基。甚至更較佳的是，每個R9 獨立地選自由以下項組成之群組：鹵素和C1 -C4 烷基。Preferably, each R 9 is independently selected from the group consisting of halogen, cyano, -N(R 6 ) 2 , C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl and C 1 -C 4 haloalkoxy. More preferably, each R 9 is independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 haloalkyl. Even more preferably, each R 9 is independently selected from the group consisting of halogen and C 1 -C 4 alkyl.
X選自由以下項組成之群組：C3 -C6 環烷基、苯基、包含1、2、3或4個單獨地選自N、O和S的雜原子的5員或6員雜芳基以及包含1、2或3個單獨地選自N、O和S的雜原子的4員至6員雜環基，並且其中該環烷基、苯基、雜芳基或雜環基部分視需要被1或2個選自R9 的可以相同或不同的取代基取代，並且其中前述CR1 R2 、Q和Z部分可以附接在該環烷基、苯基、雜芳基或雜環基部分的任何位置。X is selected from the group consisting of C 3 -C 6 cycloalkyl, phenyl, 5-membered or 6-membered heteroatoms containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S Aryl and 4-membered to 6-membered heterocyclic groups containing 1, 2 or 3 heteroatoms independently selected from N, O and S, and wherein the cycloalkyl, phenyl, heteroaryl or heterocyclyl moiety It is optionally substituted by 1 or 2 substituents selected from R 9 which may be the same or different, and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached to the cycloalkyl, phenyl, heteroaryl or hetero Any position of the ring base part.
較佳的是，X選自由以下項組成之群組：苯基和包含1或2個單獨地選自N和O的雜原子的4員至6員雜環基，並且其中該苯基或雜環基部分視需要被1或2個選自R9 的可以相同或不同的取代基取代，並且其中前述CR1 R2 、Q和Z部分可以附接在該苯基或雜環基部分的任何位置。Preferably, X is selected from the group consisting of: a phenyl group and a 4-membered to 6-membered heterocyclic group containing 1 or 2 heteroatoms independently selected from N and O, and wherein the phenyl or hetero The cyclic moiety is optionally substituted with 1 or 2 substituents selected from R 9 which may be the same or different, and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached to any of the phenyl or heterocyclic moieties position.
更較佳的是，X係包含1或2個單獨地選自N和O的雜原子的4員至6員雜環基，並且其中該雜環基部分視需要被1或2個選自R9 的可以相同或不同的取代基取代，並且其中前述CR1 R2 、Q和Z部分可以附接在該雜環基部分的任何位置。More preferably, X is a 4-membered to 6-membered heterocyclic group containing 1 or 2 heteroatoms independently selected from N and O, and wherein the heterocyclic group portion is optionally selected by 1 or 2 from R 9 may be substituted with the same or different substituents, and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached at any position of the heterocyclic moiety.
在一個實施方式中，X係包含1個雜原子的5員雜環基，其中該雜原子係N，並且其中前述CR1 R2 、Q和Z部分可以附接在該雜環基部分的任何位置。較佳的是，X係包含1個雜原子的5員雜環基，其中該雜原子係N，並且其中前述CR1 R2 和Q部分與N原子相鄰附接並且Z部分與N原子附接。In one embodiment, X is a 5-membered heterocyclic group containing 1 heteroatom, wherein the heteroatom is N, and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached to any of the heterocyclic moieties position. Preferably, X is a 5-membered heterocyclic group containing 1 heteroatom, wherein the heteroatom is N, and wherein the aforementioned CR 1 R 2 and Q moieties are attached adjacent to the N atom and the Z moiety is attached to the N atom. Pick up.
在另一個實施方式中，X係視需要被1或2個選自R9 的可以相同或不同的取代基取代的苯基，並且其中前述CR1 R2 、Q和Z部分可以附接在該苯基部分的任何位置。較佳的是，X係苯基，並且前述CR1 R2 和Q部分以對位與Z部分附接。In another embodiment, X is a phenyl group optionally substituted with 1 or 2 substituents selected from R 9 which may be the same or different, and wherein the aforementioned CR 1 R 2 , Q and Z moieties may be attached to the Any position of the phenyl moiety. Preferably, X is a phenyl group, and the aforementioned CR 1 R 2 and Q moieties are attached to the Z moiety in a para position.
n係0或1。較佳的是，n為0。n is 0 or 1. Preferably, n is zero.
Z選自由以下項組成之群組：-C(O)OR10 、-CH2 OH、-CHO、-C(O)NHOR11 、-C(O)NHCN、-OC(O)NHOR11 、-OC(O)NHCN、-NR6 C(O)NHOR11 、-NR6 C(O)NHCN、-C(O)NHS(O)2 R12 、-OC(O)NHS(O)2 R12 、-NR6 C(O)NHS(O)2 R12 、-S(O)2 OR10 、-OS(O)2 OR10 、-NR6 S(O)2 OR10 、-NR6 S(O)OR10 、-NHS(O)2 R14 、-S(O)OR10 、-OS(O)OR10 、-S(O)2 NHCN、-S(O)2 NHC(O)R18 、-S(O)2 NHS(O)2 R12 、-OS(O)2 NHCN、-OS(O)2 NHS(O)2 R12 、-OS(O)2 NHC(O)R18 、-NR6 S(O)2 NHCN、-NR6 S(O)2 NHC(O)R18 、-N(OH)C(O)R15 、-ONHC(O)R15 、-NR6 S(O)2 NHS(O)2 R12 、-P(O)(R13 )(OR10 )、-P(O)H(OR10 )、-OP(O)(R13 )(OR10 )、-NR6 P(O)(R13 )(OR10 )和四唑。Z is selected from the group consisting of: -C(O)OR 10 , -CH 2 OH, -CHO, -C(O)NHOR 11 , -C(O)NHCN, -OC(O)NHOR 11 ,- OC(O)NHCN, -NR 6 C(O)NHOR 11 , -NR 6 C(O)NHCN, -C(O)NHS(O) 2 R 12 , -OC(O)NHS(O) 2 R 12 , -NR 6 C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 , -OS(O) 2 OR 10 , -NR 6 S(O) 2 OR 10 , -NR 6 S( O)OR 10 , -NHS(O) 2 R 14 , -S(O)OR 10 , -OS(O)OR 10 , -S(O) 2 NHCN, -S(O) 2 NHC(O)R 18 , -S(O) 2 NHS(O) 2 R 12 , -OS(O) 2 NHCN, -OS(O) 2 NHS(O) 2 R 12 , -OS(O) 2 NHC(O)R 18 , -NR 6 S(O) 2 NHCN, -NR 6 S(O) 2 NHC(O)R 18 , -N(OH)C(O)R 15 , -ONHC(O)R 15 , -NR 6 S( O) 2 NHS(O) 2 R 12 , -P(O)(R 13 )(OR 10 ), -P(O)H(OR 10 ), -OP(O)(R 13 )(OR 10 ), -NR 6 P(O)(R 13 )(OR 10 ) and tetrazole.
較佳的是，Z選自由以下項組成之群組：-C(O)OR10 、-C(O)NHOR11 、-OC(O)NHOR11 、-NR6 C(O)NHOR11 、-C(O)NHS(O)2 R12 、-OC(O)NHS(O)2 R12 、-NR6 C(O)NHS(O)2 R12 、-S(O)2 OR10 、-OS(O)2 OR10 、-NR6 S(O)2 OR10 、-NR6 S(O)OR10 、-NHS(O)2 R14 、-S(O)OR10 、-OS(O)OR10 、-S(O)2 NHC(O)R18 、-S(O)2 NHS(O)2 R12 、-OS(O)2 NHS(O)2 R12 、-OS(O)2 NHC(O)R18 、-NR6 S(O)2 NHC(O)R18 、-N(OH)C(O)R15 、-ONHC(O)R15 、-NR6 S(O)2 NHS(O)2 R12 、-P(O)(R13 )(OR10 )、-P(O)H(OR10 )、-OP(O)(R13 )(OR10 )以及-NR6 P(O)(R13 )(OR10 )。Preferably, Z is selected from the group consisting of: -C(O)OR 10 , -C(O)NHOR 11 , -OC(O)NHOR 11 , -NR 6 C(O)NHOR 11 ,- C(O)NHS(O) 2 R 12 , -OC(O)NHS(O) 2 R 12 , -NR 6 C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 ,- OS(O) 2 OR 10 , -NR 6 S(O) 2 OR 10 , -NR 6 S(O)OR 10 , -NHS(O) 2 R 14 , -S(O)OR 10 , -OS(O )OR 10 , -S(O) 2 NHC(O)R 18 , -S(O) 2 NHS(O) 2 R 12 , -OS(O) 2 NHS(O) 2 R 12 , -OS(O) 2 NHC(O)R 18 , -NR 6 S(O) 2 NHC(O)R 18 , -N(OH)C(O)R 15 , -ONHC(O)R 15 , -NR 6 S(O) 2 NHS(O) 2 R 12 , -P(O)(R 13 )(OR 10 ), -P(O)H(OR 10 ), -OP(O)(R 13 )(OR 10 ) and -NR 6 P(O)(R 13 )(OR 10 ).
更較佳的是，Z選自由以下項組成之群組：-C(O)OR10 、-C(O)NHOR11 、-C(O)NHS(O)2 R12 、-S(O)2 OR10 、-OS(O)2 OR10 、-NR6 S(O)2 OR10 、-NHS(O)2 R14 、-S(O)OR10 以及-P(O)(R13 )(OR10 )。More preferably, Z is selected from the group consisting of: -C(O)OR 10 , -C(O)NHOR 11 , -C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 , -OS(O) 2 OR 10 , -NR 6 S(O) 2 OR 10 , -NHS(O) 2 R 14 , -S(O)OR 10 and -P(O)(R 13 ) (OR 10 ).
甚至更較佳的是，Z選自由以下項組成之群組：-C(O)OR10 、-C(O)NHS(O)2 R12 、-S(O)2 OR10 以及-P(O)(R13 )(OR10 )。Even more preferably, Z is selected from the group consisting of -C(O)OR 10 , -C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10, and -P( O)(R 13 )(OR 10 ).
甚至還更較佳的是，Z選自由以下項組成之群組：-C(O)OH、-C(O)OCH3 、-C(O)OCH2 CH3 、-C(O)OCH(CH3 )2 、-C(O)OC(CH3 )3 、-C(O)OCH2 C6 H5 、-C(O)OC6 H5 、-C(O)NHS(O)2 CH3 、-S(O)2 OH、-P(O)(OH)( OCH2 CH3 )以及-P(O)(OCH2 CH3 )(OCH2 CH3 )。Even more preferably, Z is selected from the group consisting of: -C(O)OH, -C(O)OCH 3 , -C(O)OCH 2 CH 3 , -C(O)OCH( CH 3 ) 2 , -C(O)OC(CH 3 ) 3 , -C(O)OCH 2 C 6 H 5 , -C(O)OC 6 H 5 , -C(O)NHS(O) 2 CH 3. -S(O) 2 OH, -P(O)(OH)( OCH 2 CH 3 ) and -P(O)(OCH 2 CH 3 )(OCH 2 CH 3 ).
最較佳的是，Z係-C(O)OH或-S(O)2 OH。Most preferably, Z is -C(O)OH or -S(O) 2 OH.
R10 選自由以下項組成之群組：氫、C1 -C6 烷基、苯基和苄基，並且其中該苯基或苄基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R10 選自由以下項組成之群組：氫、C1 -C6 烷基、苯基和苄基。更較佳的是，R10 選自由以下項組成之群組：氫和C1 -C6 烷基。最較佳的是，R10 係氫。R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl, and wherein the phenyl or benzyl group is optionally composed of 1 , 2 or 3 R which may be the same or different 9 Substituents are substituted. Preferably, R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl. More preferably, R 10 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Most preferably, R 10 is hydrogen.
R11 選自由以下項組成之群組：氫、C1 -C6 烷基和苯基，並且其中該苯基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R11 選自由以下項組成之群組：氫、C1 -C6 烷基和苯基。更較佳的是，R11 選自由以下項組成之群組：氫和C1 -C6 烷基。甚至更較佳的是，R11 係C1 -C6 烷基。最較佳的是，R11 係甲基。R 11 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and phenyl, and wherein the phenyl is optionally substituted with 1, 2 or 3 substituents of R 9 which may be the same or different. Preferably, R 11 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl and phenyl. More preferably, R 11 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Even more preferably, R 11 is a C 1 -C 6 alkyl group. Most preferably, R 11 is a methyl group.
R12 選自由以下項組成之群組：C1 -C6 烷基、C1 -C6 鹵代烷基、C1 -C6 烷氧基、-OH、-N(R6 )2 和苯基，並且其中該苯基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R12 選自由以下項組成之群組：C1 -C6 烷基、C1 -C6 鹵代烷基、C1 -C6 烷氧基、-OH、-N(R6 )2 和苯基。更較佳的是，R12 選自由以下項組成之群組：C1 -C6 烷基、C1 -C6 鹵代烷基和-N(R6 )2 。甚至更較佳的是，R12 選自由以下項組成之群組：甲基、-N(Me)2 和三氟甲基。最較佳的是，R12 係甲基。R 12 is selected from the group consisting of: C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -OH, -N(R 6 ) 2 and phenyl, And wherein the phenyl group is optionally substituted with 1, 2 or 3 R 9 substituents which may be the same or different. Preferably, R 12 is selected from the group consisting of: C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -OH, -N(R 6 ) 2 and phenyl. More preferably, R 12 is selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, and -N(R 6 ) 2 . Even more preferably, R 12 is selected from the group consisting of methyl, -N(Me) 2 and trifluoromethyl. Most preferably, R 12 is a methyl group.
R13 選自由以下項組成之群組：-OH、C1 -C6 烷基、C1 -C6 烷氧基和苯基。較佳的是，R13 選自由以下項組成之群組：-OH、C1 -C6 烷基和C1 -C6 烷氧基。更較佳的是，R13 選自由以下項組成之群組：-OH和C1 -C6 烷氧基。甚至更較佳的是，R13 選自由以下項組成之群組：-OH、甲氧基和乙氧基。最較佳的是，R13 係-OH。R 13 is selected from the group consisting of -OH, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and phenyl. Preferably, R 13 is selected from the group consisting of -OH, C 1 -C 6 alkyl and C 1 -C 6 alkoxy. More preferably, R 13 is selected from the group consisting of -OH and C 1 -C 6 alkoxy. Even more preferably, R 13 is selected from the group consisting of -OH, methoxy and ethoxy. Most preferably, R 13 is -OH.
R14 係C1 -C6 鹵代烷基。較佳的是，R14 係三氟甲基。R 14 is a C 1 -C 6 haloalkyl group. Preferably, R 14 is a trifluoromethyl group.
R15 選自由以下項組成之群組：C1 -C6 烷基和苯基，並且其中該苯基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R15 選自由以下項組成之群組：C1 -C6 烷基和苯基。更較佳的是，R15 係C1 -C6 烷基。最較佳的是，R15 係甲基。R 15 is selected from the group consisting of C 1 -C 6 alkyl and phenyl, and wherein the phenyl is optionally substituted with 1, 2 or 3 R 9 substituents which may be the same or different. Preferably, R 15 is selected from the group consisting of C 1 -C 6 alkyl and phenyl. More preferably, R 15 is a C 1 -C 6 alkyl group. Most preferably, R 15 is a methyl group.
R15a 係苯基，其中該苯基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R15a 係視需要被1個R9 取代基取代的苯基。更較佳的是，R15a 係苯基。R 15a is a phenyl group, wherein the phenyl group is optionally substituted with 1, 2 or 3 R 9 substituents which may be the same or different. Preferably, R 15a is a phenyl group optionally substituted with one R 9 substituent. More preferably, R 15a is a phenyl group.
R16 和R17 獨立地選自由以下項組成之群組：氫和C1 -C6 烷基。較佳的是，R16 和R17 獨立地選自由以下項組成之群組：氫和甲基。R 16 and R 17 are independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl. Preferably, R 16 and R 17 are independently selected from the group consisting of hydrogen and methyl.
可替代地，R16 和R17 與它們所附接的氮原子一起形成4員至6員雜環基環，該雜環基環視需要包含一個另外的單獨地選自N、O和S的雜原子。較佳的是，R16 和R17 與它們所附接的氮原子一起形成5員至6員雜環基環，該雜環基環視需要包含一個另外的單獨地選自N和O的雜原子。更較佳的是，R16 和R17 與它們所附接的氮原子一起形成吡咯啶基、㗁唑啶基、咪唑啶基、哌啶基、哌𠯤基或𠰌啉基基團。Alternatively, R 16 and R 17 together with the nitrogen atom to which they are attached form a 4-membered to 6-membered heterocyclyl ring, which optionally contains an additional heterocyclic ring independently selected from N, O and S. atom. Preferably, R 16 and R 17 together with the nitrogen atom to which they are attached form a 5-membered to 6-membered heterocyclic ring, and the heterocyclic ring optionally contains an additional heteroatom independently selected from N and O . More preferably, R 16 and R 17 together with the nitrogen atom to which they are attached form a pyrrolidinyl, azolidine, imidazolidinyl, piperidinyl, piperidinyl, or pyrrolidinyl group.
R18 選自由以下項組成之群組：氫、C1 -C6 烷基、C1 -C6 鹵代烷基、C1 -C6 烷氧基、-N(R6 )2 和苯基，並且其中該苯基視需要被1、2或3個可以相同或不同的R9 取代基取代。較佳的是，R18 選自由以下項組成之群組：氫、C1 -C6 烷基、C1 -C6 鹵代烷基、C1 -C6 烷氧基、-N(R6 )2 和苯基。更較佳的是，R18 選自由以下項組成之群組：氫、C1 -C6 烷基和C1 -C6 鹵代烷基。進一步更較佳的是，R18 選自由以下項組成之群組：C1 -C6 烷基和C1 -C6 鹵代烷基。最較佳的是，R18 係甲基或三氟甲基。R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -N(R 6 ) 2 and phenyl, and Wherein the phenyl group is optionally substituted with 1, 2 or 3 R 9 substituents which may be the same or different. Preferably, R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, -N(R 6 ) 2 And phenyl. More preferably, R 18 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, and C 1 -C 6 haloalkyl. More preferably, R 18 is selected from the group consisting of: C 1 -C 6 alkyl and C 1 -C 6 haloalkyl. Most preferably, R 18 is methyl or trifluoromethyl.
整數r係0、1或2。較佳的是，r係0或2。 在一組較佳的實施方式中，在本發明的根據式 (I) 之化合物中， R1 係氫或C1 -C6 烷基； R2 係氫或甲基； Q係(CR1a R2b )m ； m係0、1或2； R1a 和R2b 獨立地選自由以下項組成之群組：氫、C1 -C6 烷基、-OH和-NH2 ； R3 、R4 和R5 獨立地選自由以下項組成之群組：氫和C1 -C6 烷基； 每個R6 獨立地選自氫和甲基； 每個R7 係C1 -C6 烷基； A係包含1或2個氮原子的10員雜芳基並且其中該雜芳基可以視需要被1或2個可以相同或不同的R8 取代基在C上取代；或者A係包含氮原子和硫或氧原子的9員雜芳基，其中該雜芳基可以視需要被1或2個可以相同或不同的R8 取代基在C上取代並且視需要被1或2個可以相同或不同的R8 取代基在N上取代； 當R8 附接至C時，它較佳的是獨立地選自由以下項組成之群組：鹵素、硝基、氰基、-NH2 、-NHR7 、-N(R7 )2 、-OH、-OR7 、-S(O)r R15 、-NR6 S(O)2 R15 、-C(O)OR10 、-C(O)R15 、-C(O)NR16 R17 、-S(O)2 NR16 R17 、C1 -C6 烷基以及C1 -C6 鹵代烷基；更較佳的是當R8 附接至C時，它係氫、鹵素或C1 -C6 烷基，最較佳的是氫或甲基； 當R8 附接至N時，它較佳的是C1 -C6 烷基，最較佳的是甲基； n係0； Z選自由以下項組成之群組：-C(O)OR10 、-C(O)NHS(O)2 R12 、-S(O)2 OR10 以及-P(O)(R13 )(OR10 )； R10 選自由以下項組成之群組：氫、C1 -C6 烷基、苯基以及苄基； R12 選自由以下項組成之群組：C1 -C6 烷基、C1 -C6 鹵代烷基和-N(R6 )2 ； R13 選自由以下項組成之群組：-OH和C1 -C6 烷氧基； R15 係C1 -C6 烷基； R16 和R17 獨立地選自由以下項組成之群組：氫和甲基；並且 r係0或2。The integer r is 0, 1, or 2. Preferably, r is 0 or 2. In a set of preferred embodiments, in the compound according to formula (I) of the present invention, R 1 is hydrogen or C 1 -C 6 alkyl; R 2 is hydrogen or methyl; Q is (CR 1a R 2b ) m ; m is 0, 1, or 2; R 1a and R 2b are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, -OH and -NH 2 ; R 3 , R 4 And R 5 are independently selected from the group consisting of: hydrogen and C 1 -C 6 alkyl; each R 6 is independently selected from hydrogen and methyl; each R 7 is a C 1 -C 6 alkyl; A series contains a 10-membered heteroaryl group containing 1 or 2 nitrogen atoms and wherein the heteroaryl group may be optionally substituted with 1 or 2 R 8 substituents which may be the same or different on C; or series A contains a nitrogen atom and 9 sulfur or oxygen atom heteroaryl, wherein the heteroaryl may optionally be substituted with 1 or 2 may be the same or different R 8 substituents on the C and optionally substituted with 1 or 2 may be the same or different, The R 8 substituent is substituted on N; when R 8 is attached to C, it is preferably independently selected from the group consisting of halogen, nitro, cyano, -NH 2 , -NHR 7 , -N(R 7 ) 2 , -OH, -OR 7 , -S(O) r R 15 , -NR 6 S(O) 2 R 15 , -C(O)OR 10 , -C(O)R 15 , -C(O)NR 16 R 17 , -S(O) 2 NR 16 R 17 , C 1 -C 6 alkyl and C 1 -C 6 haloalkyl; more preferably when R 8 is attached to C When R 8 is attached to N, it is preferably C 1 -C 6 alkyl, most preferably hydrogen or methyl; when R 8 is attached to N, it is preferably C 1 -C 6 alkyl, most preferably Preferred is methyl; n is 0; Z is selected from the group consisting of -C(O)OR 10 , -C(O)NHS(O) 2 R 12 , -S(O) 2 OR 10 and -P(O)(R 13 )(OR 10 ); R 10 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, phenyl and benzyl; R 12 is selected from the group consisting of Group: C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and -N(R 6 ) 2 ; R 13 is selected from the group consisting of: -OH and C 1 -C 6 alkoxy; R 15 is C 1 -C 6 alkyl; R 16 and R 17 are independently selected from the group consisting of hydrogen and methyl; and r is 0 or 2.
更較佳的是， R1 係氫或甲基； R2 係氫或甲基； Q係(CR1a R2b )m ； m係1或2； R1a 和R2b 獨立地選自由以下項組成之群組：氫和甲基； R3 、R4 和R5 獨立地選自由以下項組成之群組：氫和甲基； A選自由以下項組成之群組：式A-I至A-XIII，並且p為0、1或2，更較佳的是0或1，最較佳的是0；More preferably, R 1 is hydrogen or methyl; R 2 is hydrogen or methyl; Q is (CR 1a R 2b ) m ; m is 1 or 2; R 1a and R 2b are independently selected from the following items The group of: hydrogen and methyl; R 3 , R 4 and R 5 are independently selected from the group consisting of: hydrogen and methyl; A is selected from the group consisting of: formula AI to A-XIII, And p is 0, 1, or 2, more preferably 0 or 1, and most preferably 0;
當R8 附接至C時，其各自獨立地選自由以下項組成之群組：氯、氟、氰基、-NH2 、-N(Me)2 、-OH、-OMe、-S(O)2 Me、-C(O)OMe、-C(O)OH、-C(O)Me、-C(O)NH2 、-C(O)NHMe、-C(O)N(Me)2 、甲基以及三氟甲基；當R8 附接至N時，它為C1-C6 烷基，或最較佳的是甲基。 n係0；並且When R 8 is attached to C, they are each independently selected from the group consisting of: chlorine, fluorine, cyano, -NH 2 , -N(Me) 2 , -OH, -OMe, -S(O ) 2 Me, -C(O)OMe, -C(O)OH, -C(O)Me, -C(O)NH 2 , -C(O)NHMe, -C(O)N(Me) 2 , Methyl and trifluoromethyl; when R 8 is attached to N, it is C1-C 6 alkyl, or most preferably methyl. n is 0; and
Z選自由以下項組成之群組：-C(O)OH、-C(O)OCH3 、-C(O)OCH2 CH3 、-C(O)OCH(CH3 )2 、-C(O)OC(CH3 )3 、-C(O)OCH2 C6 H5 、-C(O)OC6 H5 、-C(O)NHS(O)2 CH3 、-S(O)2 OH、-P(O)(OH)( OCH2 CH3 )以及-P(O)(OCH2 CH3 )(OCH2 CH3 )。Z is selected from the group consisting of: -C(O)OH, -C(O)OCH 3 , -C(O)OCH 2 CH 3 , -C(O)OCH(CH 3 ) 2 , -C( O)OC(CH 3 ) 3 , -C(O)OCH 2 C 6 H 5 , -C(O)OC 6 H 5 , -C(O)NHS(O) 2 CH 3 , -S(O) 2 OH, -P(O)(OH)( OCH 2 CH 3 ), and -P(O)(OCH 2 CH 3 )(OCH 2 CH 3 ).
在另一組較佳的實施方式中，根據式 (I) 之化合物選自下面具有式 (I-aa) 至 (I-cm) 之化合物。
Z選自由以下項組成之群組：-C(O)OH、-C(O)OCH3 、-C(O)OCH2 CH3 、-C(O)OCH(CH3 )2 、-C(O)OC(CH3 )3 、-C(O)OCH2 C6 H5 、-C(O)OC6 H5 、-C(O)NHS(O)2 CH3 、-S(O)2 OH、-P(O)(OH)( OCH2 CH3 )以及-P(O)(OCH2 CH3 )(OCH2 CH3 )，較佳的是Z係-C(O)OH或-S(O)2 OH。Z is selected from the group consisting of: -C(O)OH, -C(O)OCH 3 , -C(O)OCH 2 CH 3 , -C(O)OCH(CH 3 ) 2 , -C( O)OC(CH 3 ) 3 , -C(O)OCH 2 C 6 H 5 , -C(O)OC 6 H 5 , -C(O)NHS(O) 2 CH 3 , -S(O) 2 OH, -P(O)(OH)( OCH 2 CH 3 ) and -P(O)(OCH 2 CH 3 )(OCH 2 CH 3 ), preferably Z series -C(O)OH or -S (O) 2 OH.
在化合物I-aa至I-cm中較佳的是化合物I-aa、I-ab、I-af、I-am、I-ba、I-bb、I-bf、I-bm、I-ca、I-cb、I-cf和I-cm。Preferred among compounds I-aa to I-cm are compounds I-aa, I-ab, I-af, I-am, I-ba, I-bb, I-bf, I-bm, I-ca , I-cb, I-cf and I-cm.
還提供了一種用於製備具有式 (I) 之化合物之方法：
根據本發明，還提供了如本文所定義的具有式 (J) 之化合物在製造如本文所定義的具有式 (I) 之化合物的方法中之用途。較佳的是，在具有式 (J) 之化合物中，M'係有機錫烷、有機硼酸、有機硼酸的酯或有機三氟硼酸酯。更較佳的是，在具有式 (J) 之化合物中，M'係有機錫烷。最較佳的是，在具有式 (J) 之化合物中，M'係三丁基錫烷。According to the present invention, there is also provided the use of a compound of formula (J) as defined herein in a method for producing a compound of formula (I) as defined herein. Preferably, in the compound of formula (J), M'is an organotinane, organoboric acid, ester of organoboric acid, or organotrifluoroborate. More preferably, in the compound of formula (J), M'is an organotinane. Most preferably, in the compound of formula (J), M'is tributylstannane.
在本發明的另一個實施方式中，還提供了如本文所定義的具有式 (X) 之化合物在製造如本文所定義的具有式 (I) 之化合物的方法中之用途。In another embodiment of the present invention, there is also provided the use of the compound of formula (X) as defined herein in the method of manufacturing the compound of formula (I) as defined herein.
應當理解，具有式 (I) 之化合物能以‘procidal形式’存在/製造，其中它們包含基團‘G’。此類化合物在本文中稱為具有式 (I-IV) 之化合物。
G係可以藉由任何適當的機制在植物中除去的基團，該機制包括但不限於代謝和化學降解，以得到具有式 (I-I)、(I-II) 或 (I-III) 之化合物，其中Z含有酸性質子，例如參見下面的流程：
當此類G基團可以被認為係「procidal」，並且因此一旦除去就產生活性除草化合物時，包含此類基團的化合物本身也可以展現出除草活性。在此類情況下，在具有式 (I-IV) 之化合物中，Z-G可以包括但不限於下面的 (G1) 至 (G7) 中的任何一個，並且E指示與具有式 (I) 之化合物的剩餘部分的附接點：
以下表1至表12中的化合物闡明本發明的化合物。技術人員將理解，具有式 (I) 之化合物可以如上文所述的作為農學上可接受的鹽、兩性離子或農學上可接受的兩性離子鹽存在。
[表 1
]：
此表揭露了53種具有式 (T-1) 之特定化合物：
本發明的化合物可以根據下列流程製備，其中除非另外明確說明，取代基n、m、r、A、Q、X、Z、R1 、R2 、R1a 、R2b 、R2 、R3 、R4 、R5 、R6 、R7 、R8 、R9 、R10 、R11 、R12 、R13 、R14 、R15 、R16 、R17 和R18 如上文所定義。因此，前述表1至表15的化合物能以類似的方式獲得。The compounds of the present invention can be prepared according to the following scheme, in which unless expressly stated otherwise, the substituents n, m, r, A, Q, X, Z, R 1 , R 2 , R 1a , R 2b , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are as defined above. Therefore, the compounds of the aforementioned Tables 1 to 15 can be obtained in a similar manner.
具有式 (I) 之化合物可以藉由在合適的溫度下，在合適的溶劑中，將具有式 (X) 化合物（其中R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）用具有式 (W) 之合適烷基化劑（其中R1
、R2
、Q、X、n和Z如針對具有式 (I) 之化合物所定義，並且LG係合適的脫離基，例如鹵化物或擬鹵化物，如三氟甲磺酸酯、甲磺酸酯或甲苯磺酸酯）烷基化來製備，如反應流程1中所述。示例性條件包括在-78°C與150°C之間的溫度下，將具有式 (X) 之化合物與具有式 (W) 之烷基化劑在諸如丙酮、二氯甲烷、二氯乙烷、N,N
-二甲基甲醯胺、乙腈、1,4-二㗁𠮿、水、乙酸或三氟乙酸等溶劑或溶劑混合物中進行攪拌。具有式 (W) 之烷基化劑可以包括但不限於溴乙酸、溴乙酸甲酯、3-溴丙酸、3-溴丙酸甲酯、2-溴-N-甲氧基乙醯胺、2-溴乙磺酸鈉、2-(三氟甲基磺醯氧基)乙磺酸2,2-二甲基丙酯、2-溴-N-甲磺醯基乙醯胺、3-溴-N-甲磺醯基丙醯胺、三氟甲磺酸二甲氧基磷醯基甲酯、3-溴丙基膦酸二甲酯、3-氯-2,2-二甲基-丙酸和2-溴乙基膦酸二乙酯。此類烷基化劑和相關化合物在文獻中是已知的，或者可以藉由已知的文獻方法製備。隨後可以將可描述為N-烷基酸的酯（其包括但不限於羧酸、膦酸、次膦酸、磺酸和亞磺酸的酯）的具有式 (I) 之化合物藉由在0°C與100°C之間的合適溫度下，在合適的溶劑中，用合適的試劑（例如，水性鹽酸或三甲基矽基溴化物）進行處理來部分或完全水解。反應流程 1 
另外，具有式 (I) 之化合物可以藉由在合適的溫度下，在合適的溶劑中，使具有式 (X) 之化合物（其中R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）與適當活化的具有式 (B) 之親電子烯烴（其中Z為-S(O)2
OR10
、-P(O)(R13
)(OR10
)或-C(O)OR10
，並且R1
、R2
、R1a
、R10
和R13
如針對具有式 (I) 之化合物所定義）反應來製備。具有式 (B) 之化合物在文獻中是已知的，或者可以藉由已知的方法製備。示例性試劑包括但不限於丙烯酸、甲基丙烯酸、巴豆酸、3,3-二甲基丙烯酸、丙烯酸甲酯、乙烯磺酸、乙烯磺酸異丙酯、乙烯磺酸2,2-二甲基丙酯和乙烯基膦酸二甲酯。隨後可以將可描述為N-烷基酸的酯（其包括但不限於羧酸、膦酸、次膦酸、磺酸和亞磺酸的酯）的該等反應的直接產物藉由在合適的溫度下，在合適的溶劑中，用合適的試劑進行處理來部分或完全水解，如反應流程2中所述。反應流程 2 
在相關的反應中，具有式 (I) 之化合物（其中Q係C(R1a
R2b
)，m係1、2或3，n = 0並且Z係-S(O)2
OH、-OS(O)2
OH或-NR6
S(O)2
OH）可以藉由在合適的溫度下，在合適的溶劑中，使具有式 (X) 之化合物（其中R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）與具有式 (E)、(F) 或 (AF) 之環狀烷基化劑（其中Ya
係C(R1a
R2b
)、O或NR6
，並且R1
、R2
、R1a
和R2b
如針對具有式 (I) 之化合物所定義）反應來製備，如反應流程3中所述。合適的溶劑和合適的溫度如前所述。具有式 (E) 或 (F) 之烷基化劑可以包括但不限於1,3-丙磺酸內酯、1,4-丁磺酸內酯、乙烯硫酸酯、1,3-丙烯硫酸酯和1,2,3-氧雜四氫噻唑2,2-二氧化物。此類烷基化劑和相關化合物在文獻中是已知的，或者可以藉由已知的文獻方法製備。反應流程 3 
具有式 (I) 之化合物（其中m為0，n為0且Z為-S(O)2
OH）可以由具有式 (I) 之化合物（其中m為0，n為0且Z為C(O)OR10
），藉由在合適的溫度下，在合適的溶劑中，用三甲基矽基氯磺酸酯進行處理來製備，如反應流程4中所述。較佳的條件包括在25°C與150°C之間的溫度下在純三甲基矽基氯磺酸酯中加熱羧酸酯先質。反應流程 4 
此外，具有式 (I) 之化合物可以藉由使具有式 (X) 之化合物（其中R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）與具有式 (WW) 之合適醇（其中R1
、R2
、Q、X、n和Z如針對具有式 (I) 之化合物所定義）在光延反應（Mitsunobu）類型條件（如Petit等人, Tet. Lett. [四面體快報]2008, 49 (22), 3663所報導的那些）下反應來製備。合適的膦包括三苯基膦，合適的偶氮二羧酸酯包括偶氮二羧酸二異丙酯，並且合適的酸包括氟硼酸、三氟甲磺酸和雙(三氟甲基磺醯基)胺，如反應流程5中所述。此類醇在文獻中是已知的，或者可以藉由已知的文獻方法製備。反應流程 5 
具有式 (I) 之化合物還可以藉由在合適的溫度（-78°C和150°C之間）下，在合適的酸存在下，在合適的溶劑或溶劑混合物中，使具有式 (C) 之化合物（其中Q、Z、X、n、R1
、R2
、R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）與具有式 (D) 之肼反應來製備，如反應流程6中所述。合適的溶劑或其混合物包括但不限於醇（如甲醇、乙醇和異丙醇）、水、水性鹽酸、水性硫酸、乙酸和三氟乙酸。具有式 (D) 之肼化合物（例如2-肼基乙磺酸2,2-二甲基丙酯）在文獻方法中是已知的，或者可以藉由已知的文獻方法製備。反應流程 6 
具有式 (C) 之化合物可以藉由在合適的溫度（-78°C和150°C之間）下，視需要在合適的鹼存在下，在合適的溶劑中，使具有式 (G) 之化合物（其中R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）與氧化劑反應來製備，如反應流程7中所述。合適的氧化劑包括但不限於溴，並且合適的溶劑包括但不限於醇，如甲醇、乙醇和異丙醇。合適的鹼包括但不限於碳酸氫鈉、碳酸鈉、碳酸氫鉀、碳酸鉀和乙酸鉀。類似的反應在文獻中是已知的（例如Hufford, D. L.; Tarbell, D. S.; Koszalka, T. R. J. Amer. Chem. Soc. [美國化學學會雜誌], 1952, 3014）。具有式 (G) 之呋喃在文獻中是已知的，或者可以使用文獻方法製備。示例性方法包括但不限於過渡金屬交叉偶合，如Stille（例如Farina, V.; Krishnamurthy, V.; Scott, W. J. Organic Reactions [有機反應雜誌], 第50卷. 1997和Gazzard, L.等人 J. Med. Chem. [藥物化學雜誌], 2015, 5053）、Suzuki-Miyaura（例如Ando, S.; Matsunaga, H.; Ishizuka, T. J. Org. Chem. [有機化學雜誌] 2017, 1266-1272和Ernst, J. B.; Rakers, L.; Glorius, F. Synthesis [合成], 2017, 260）、Negishi（例如Yang, Y.; Oldenhius, N. J.; Buchwald, S. L. Angew. Chem. Int. Ed. [應用化學國際版] 2013, 615和Braendvang, M.; Gundersen, L. Bioorg. Med. Chem. [生物有機與藥物化學] 2005, 6360）和Kumada（例如Heravi, M. M.; Hajiabbasi, P. Monatsh. Chem. [化學月報], 2012, 1575）。可以參考特定的交叉偶合反應和目標產物來選擇偶合配偶體。過渡金屬催化劑、配位基、鹼、溶劑和溫度可以參考所希望的交叉偶合來選擇，並且在文獻中是已知的。使用擬鹵素（包括但不限於三氟甲磺酸鹽、甲磺酸鹽、甲苯磺酸鹽和茴香醚）的交叉偶合反應也可以在相關條件下實現。反應流程 7 
在另一種方法中，在合適的溫度下，在合適的溶劑中，具有式 (I) 之化合物（其中Q、Z、X、R1
、R2
、R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）可以由具有式 (R) 之化合物和氧化劑製備，如反應流程8中所概述。示例性氧化劑包括但不限於2,3-二氯-5,6-二氰基-1,4-苯醌、四氯對苯醌、過錳酸鉀、二氧化錳、2,2,6,6-四甲基-1-哌啶基氧基和溴。相關反應在文獻中是已知的。反應流程 8 
在合適的溫度下，視需要在另外的過渡金屬添加劑存在下，在合適的溶劑中，具有式 (R) 之化合物（其中Q、Z、X、R1
、R2
、R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）可以由具有式 (S) 之化合物和具有式 (T) 之有機金屬化合物（包括但不限於有機鎂、有機鋰、有機銅和有機鋅試劑 (M’)）製備，如反應流程9中所概述。示例性條件包括在-78°C與100°C之間的溫度下，在0.05%-100%碘化銅存在下，在諸如四氫呋喃等的溶劑中，用具有式 (T) 之格氏試劑（Grignard）處理具有式 (S) 之化合物。具有式 (T) 之有機金屬化合物在文獻中是已知的，或者可以藉由已知的文獻方法製備。具有式 (S) 之化合物可以藉由與製備具有式 (I) 之化合物的那些類似的反應來製備。反應流程 9 
具有式 (X) 之二芳基嗒𠯤在文獻中是已知的，或者可以使用文獻方法製備。示例性方法包括但不限於具有式 (H) 和式 (J) 之化合物或可替代地具有式 (K) 和式 (L) 之化合物的過渡金屬交叉偶合，其中具有式 (J) 和式 (L) 之化合物係有機錫烷、有機硼酸或酯、有機三氟硼酸酯、有機鎂、有機銅或有機鋅 (M’)，如反應流程10中所概述。Hal定義為鹵素或擬鹵素，例如三氟甲磺酸鹽、甲磺酸鹽和甲苯磺酸鹽。此類交叉偶合包括Stille（例如Sauer, J.; Heldmann, D. K. Tetrahedron [四面體], 1998, 4297）、Suzuki-Miyaura（例如Luebbers, T.; Flohr, A.; Jolidon, S.; David-Pierson, P.; Jacobsen, H.; Ozmen, L.; Baumann, K. Bioorg. Med. Chem. Lett. [生物有機與藥物化學快報], 2011, 6554）、Negishi（例如Imahori, T.; Suzawa, K.; Kondo, Y. Heterocycles [雜環], 2008, 1057）以及Kumada（例如Heravi, M. M.; Hajiabbasi, P. Monatsh. Chem. [化學月報], 2012, 1575）。可以參考特定的交叉偶合反應和目標產物來選擇偶合配偶體。過渡金屬催化劑、配位基、鹼、溶劑和溫度可以參考所希望的交叉偶合來選擇，並且在文獻中是已知的。具有式 (H)、式 (K) 和式 (L) 之化合物在文獻中是已知的，或者可以藉由已知的文獻方法製備。反應流程 10 
具有式 (J) 之有機金屬（其係有機錫烷、有機硼酸或酯、有機三氟硼酸酯、有機鎂、有機銅或有機鋅 (M’)）可以由具有式 (XX) 之化合物（ 其中R3
、R4
和R5
如針對具有式 (I) 之化合物所定義）藉由金屬化來製備，如反應流程11中所概述。類似的反應在文獻中是已知的（例如Ramphal等人, WO 2015153683，Unsinn等人, Organic Letters [有機快報], 15(5), 1128-1131; 2013，Sadler等人, Organic & Biomolecular Chemistry [有機與生物分子化學], 12(37), 7318-7327; 2014）。可替代地，具有式 (J) 之有機金屬化合物可以由具有式 (K) 之化合物（其中R3
、R4
、R5
如針對具有式 (I) 之化合物所定義，並且Hal定義為鹵素或擬鹵素，例如三氟甲磺酸酯、甲磺酸酯和甲苯磺酸酯）製備，如流程9中所述。製備具有式 (J) 之有機錫烷的示例性條件包括在適當的溫度下，在適當的溶劑中，用三丁基錫鋰處理具有式 (K) 之化合物（例如參見WO 2010038465）。製備具有式 (J) 之有機硼酸或酯的示例性條件包括在適當的溫度下，在適當的溶劑中，在適當的過渡金屬催化劑、適當的配位基、適當的鹼存在下，用雙(頻哪醇合)二硼處理具有式 (K) 之化合物（例如KR 2015135626）。具有式 (K) 和式 (XX) 之化合物在文獻中是已知的，或者可以藉由已知方法製備。反應流程 11 
在另一種方法中，具有式 (J) 之有機金屬化合物（其中M'係有機錫烷或有機硼酸或酯）可以由具有式 (N) 之化合物和具有式 (O) 之化合物（其中R3
、R4
和R5
如針對具有式 (I) 之化合物所定義）製備，如反應流程12中所概述。此種反應的實例在文獻中是已知的，例如，Helm等人, Org. and Biomed. Chem. [有機與生物分子化學], 2006, 4 (23), 4278，Sauer等人, Eur. J. Org. Chem. [歐洲有機化學雜誌], 1998, 12, 2885以及Helm, M. D.; Moore, J. E.; Plant, A.; Harrity, J. P. A., Angew. Chem. Int. Ed. [應用化學國際版], 2005, 3889。具有式 (N) 和式 (O) 之化合物在文獻中是已知的。反應流程 12 
在適當的溫度下，在適當的溶劑中，具有式 (X) 之化合物（其中R3
、R4
、R5
和A如先前所定義）可以由具有式 (P) 和式 (O) 之化合物製備，如反應流程13中所概述。此種反應的實例在文獻中是已知的，例如，Sauer等人, Eur. J. Org. Chem. [歐洲有機化學雜誌], 1998, 12, 2885。具有式 (P) 之化合物在文獻中是已知的，或者可以藉由已知的方法製備。反應流程 13 
在另一種方法中，在適當的溫度下，在適當的溶劑中，具有式 (X) 之化合物（其中R3
、R4
、R5
和A如針對具有式 (I) 之化合物所定義）可以由具有式 (C) 之化合物和肼製備，如反應流程14中所概述。此反應也可以視需要在酸（例如水性硫酸或水性鹽酸）存在下進行。類似的反應在文獻中是已知的（例如DE 102005029094和Chen, B.; Bohnert, T.; Zhou, X.; Dedon, P. C. Chem. Res. Toxicol. [毒物學化學研究], 2004, 1406）。具有式 (C) 之化合物可以如先前所概述製備。反應流程 14 
最後，在概述於流程15中的附加方法中，具有式 (X) 之聯芳基嗒𠯤可以藉由經典的環合成方法從具有式 (U) 之化合物開始製備，其中T係可以藉由一個或多個化學步驟轉化成A的官能基，其中A如針對具有式 (I) 之化合物所定義。此類官能基包括但不限於酸、酯、醛、腈、醯胺、硫代醯胺和酮。相關轉變在文獻中是已知的。反應流程 15 
根據本發明的化合物可以按未經修飾的形式用作除草劑，但它們通常以多種方式使用配製佐劑（如載體、溶劑和表面活性物質）被配製成組成物。該等配製物可以處於不同的實體形式，例如，處於以下形式：撒粉劑、凝膠、可濕性粉劑、水可分散性顆粒劑、水可分散性片劑、發泡顆粒、可乳化的濃縮物、微可乳化濃縮物、水包油乳劑、可流動油、水性分散體、油性分散體、懸乳劑、膠囊懸浮液、可乳化的顆粒劑、可溶性液體、水可溶性濃縮物（以水或水混溶性有機溶劑作為載體）、浸漬的聚合物膜或處於已知的其他形式，例如從Manual on Development and Use of FAO and WHO Specifications for Pesticides [關於殺有害生物劑的FAO和WHO標準的發展和使用的手冊]，聯合國，第1版，二次修訂（2010）中已知的。對於水溶性化合物，較佳的是可溶性液體、水溶性濃縮物或水溶性顆粒。此類配製物可以直接使用或者可以使用前稀釋再使用。可以用例如水、液體肥料、微量營養素、生物有機體、油或溶劑來進行稀釋。The compounds according to the present invention can be used as herbicides in an unmodified form, but they are usually formulated into compositions in a variety of ways using formulation adjuvants such as carriers, solvents and surface-active substances. These formulations can be in different physical forms, for example, in the following forms: dusting agents, gels, wettable powders, water-dispersible granules, water-dispersible tablets, foamed granules, emulsifiable concentrates Concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (in water or water Miscible organic solvents as a carrier), impregnated polymer membranes or in other known forms, for example from Manual on Development and Use of FAO and WHO Specifications for Pesticides [Development and use of FAO and WHO standards for pesticides Manual], United Nations, 1st edition, second revision (2010). For water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble particles are preferred. Such formulations can be used directly or can be diluted before use. It can be diluted with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.
可以藉由例如將活性成分與配製佐劑混合來製備該等配製物以便獲得處於精細分散固體、顆粒、溶液、分散體或乳劑形式的組成物。該等活性成分還可以與其他佐劑（例如精細分散固體、礦物油、植物或動物來源的油、改性的植物或動物來源的油、有機溶劑、水、表面活性物質或其組合）來一起配製。These formulations can be prepared by, for example, mixing the active ingredient with a formulation adjuvant in order to obtain the composition in the form of a finely divided solid, particle, solution, dispersion or emulsion. The active ingredients can also be combined with other adjuvants (such as finely divided solids, mineral oil, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface active substances, or combinations thereof). Preparation.
該等活性成分還可以被包含於非常精細的微膠囊中。微膠囊在多孔載體中含有活性成分。這使活性成分能以受控的量值釋放（例如，緩慢釋放）到環境中。微膠囊通常具有從0.1至500微米的直徑。它們含有的活性成分的量按重量計係膠囊重量的約從25%至95%。該等活性成分可以處於整體性的固體的形式、處於固體或液體分散體中的精細顆粒的形式或處於適合溶液的形式。包囊的膜可以包括例如天然的或合成的橡膠、纖維素、苯乙烯/丁二烯共聚物、聚丙烯腈、聚丙烯酸酯、聚酯、聚醯胺、聚脲、聚胺酯或經化學改性的聚合物以及澱粉黃原酸酯、或熟悉該項技術者已知的其他聚合物。可替代地，可以形成非常精細的微膠囊，其中活性成分在基礎物質的固體基質中是以精細分散顆粒的形式被包含的，但該等微膠囊本身未經包裹。These active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released into the environment in a controlled amount (for example, slow release). Microcapsules generally have a diameter from 0.1 to 500 microns. They contain active ingredients in amounts ranging from 25% to 95% by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated film may include, for example, natural or synthetic rubber, cellulose, styrene/butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified And starch xanthate, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely dispersed particles in the solid matrix of the basic substance, but the microcapsules themselves are not encapsulated.
適合於製備根據本發明的該等組成物的配製佐劑本身係已知的。作為液體載體可以使用：水、甲苯、二甲苯、石油醚、植物油、丙酮、甲基乙基酮、環己酮、酸酐、乙腈、乙醯苯、乙酸戊酯、2-丁酮、碳酸丁烯酯、氯苯、環己烷、環己醇、乙酸烷基酯、二丙酮醇、1,2-二氯丙烷、二乙醇胺、對-二乙基苯、二甘醇、松脂酸二乙二醇酯、二甘醇丁基醚、二甘醇乙基醚、二甘醇甲醚、N,N -二甲基甲醯胺、二甲基亞碸、1,4-二㗁𠮿、二丙二醇、二丙二醇甲基醚、雙丙甘醇二苯甲酸酯、二丙二醇、烷基吡咯啶酮、乙酸乙酯、2-乙基己醇、碳酸乙烯酯、1,1,1-三氯乙烷、2-庚酮、α-蒎烯、d-薴烯、乳酸乙酯、乙二醇、乙二醇丁基醚、乙二醇甲基醚、γ-丁內酯、丙三醇、乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、十六烷、己二醇、乙酸異戊基酯、乙酸異冰片基(bornyl)酯、異辛烷、異佛耳酮、異丙苯、肉豆蔻酸異丙酯、乳酸、月桂胺、亞異丙基丙酮、甲氧基丙醇、甲基異戊基酮、甲基異丁基酮、月桂酸甲酯、辛酸甲酯、油酸甲酯、二氯甲烷、間二甲苯、正己烷、正辛胺、十八烷酸、辛胺乙酸酯、油酸、油胺、鄰二甲苯、苯酚、聚乙二醇、丙酸、乳酸丙酯、碳酸丙烯酯、丙二醇、丙二醇甲基醚、對-二甲苯、甲苯、磷酸三乙酯、三乙二醇、二甲苯磺酸、石蠟、礦物油、三氯乙烯、全氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇甲基醚、二乙二醇甲基醚、甲醇、乙醇、異丙醇以及更高分子量的醇，例如戊醇、四氫呋喃醇、己醇、辛醇、乙二醇、丙二醇、甘油、N -甲基-2-吡咯啶酮等。The formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As a liquid carrier, it can be used: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetonitrile, amyl acetate, 2-butanone, butene carbonate Ester, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, rosinic acid diethylene glycol Ester, Diethylene Glycol Butyl Ether, Diethylene Glycol Ethyl Ether, Diethylene Glycol Methyl Ether, N,N -Dimethylformamide, Dimethyl Sulfide, 1,4-Diethylene Glycol, Dipropylene Glycol, Dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane , 2-Heptanone, α-pinene, d-butene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate Ester, glyceryl diacetate, glyceryl triacetate, hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, nutmeg Isopropyl acid, lactic acid, laurylamine, isopropylidene acetone, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, Dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, Propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, Amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene Alcohol, propylene glycol, glycerin, N -methyl-2-pyrrolidone, etc.
適合的固體載體係例如滑石、二氧化鈦、葉蠟石黏土、矽石、凹凸棒石黏土、矽藻土、石灰石、碳酸鈣、膨潤土、鈣蒙脫土、棉籽殼、小麥粉、大豆粉、浮石、木粉、經研磨的胡桃殼、木質素和類似的物質。Suitable solid carrier systems such as talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husk, wheat flour, soybean flour, pumice, Wood flour, ground walnut shells, lignin and similar substances.
許多表面活性物質可以有利地用在固體和液體配製物兩者中，尤其是在使用前可被載體稀釋的那些配製物中。表面活性物質可以是陰離子的、陽離子的、非離子的或聚合的並且它們可以用作乳化劑、濕潤劑或懸浮劑或用於其他目的。典型的表面活性物質包括例如烷基硫酸酯的鹽，如十二烷基硫酸二乙醇銨；烷基芳基磺酸酯的鹽，如十二烷基苯磺酸鈣；烷基酚/氧化烯加成產物，如乙氧基化壬基苯酚；醇/氧化烯加成產物，如乙氧基化十三烷醇；皂，如硬脂酸鈉；烷基萘磺酸酯的鹽，如二丁基萘磺酸鈉；磺基琥珀酸二烷基酯的鹽，如二(2-乙基己基)磺基琥珀酸鈉；山梨糖醇酯，如山梨糖醇油酸酯；季胺，如氯化十二烷基三甲基銨；脂肪酸的聚乙二醇酯，如聚乙二醇硬脂酸酯；環氧乙烷和環氧丙烷的嵌段共聚物；以及磷酸單-烷基酯和二烷基酯的鹽；以及還有其他物質，例如描述於：McCutcheon's Detergents and Emulsifiers Annual [麥卡琴清潔劑和乳化劑年鑒]，MC出版公司（MC Publishing Corp.），裡奇伍德，新澤西州（Ridgewood New Jersey）（1981）。Many surface-active substances can be advantageously used in both solid and liquid formulations, especially those formulations that can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium dodecyl sulfate; salts of alkyl aryl sulfonates, such as calcium dodecylbenzene sulfonate; alkylphenol/alkylene oxide Addition products, such as ethoxylated nonylphenol; alcohol/alkylene oxide addition products, such as ethoxylated tridecyl alcohol; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates, such as di Sodium butyl naphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium bis(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as Dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and mono-alkyl phosphates And dialkyl esters; and other substances, such as described in: McCutcheon's Detergents and Emulsifiers Annual [McCutcheon's Detergents and Emulsifiers Annual], MC Publishing Corp., Ridgewood, New Jersey State (Ridgewood New Jersey) (1981).
可以用於殺有害生物配製物的其他佐劑包括結晶抑制劑、黏度調節劑、懸浮劑、染料、抗氧化劑、發泡劑、光吸收劑、混合助劑、消泡劑、錯合劑、中和或改變pH的物質和緩衝液、腐蝕抑制劑、香料、濕潤劑、吸收增強劑、微量營養素、塑化劑、助流劑、潤滑劑、分散劑、增稠劑、防凍劑、殺微生物劑、以及液體和固體肥料。Other adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralization Or substances and buffers that change pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbicides, As well as liquid and solid fertilizers.
根據本發明的組成物可以包括添加劑，該添加劑包括植物或動物來源的油、礦物油、此類油的烷基酯或此類油與油衍生物的混合物。在根據本發明的組成物中的油添加劑的量通常是基於該待施用的混合物的從0.01%到10%。例如，可以在噴霧混合物已經製備之後將該油添加劑以所希望的濃度添加到噴霧罐中。較佳的油添加劑包括礦物油或植物來源的油，例如菜籽油、橄欖油或葵花籽油；乳化的植物油；植物來源的油的烷基酯，例如甲基衍生物；或動物來源的油，如魚油或牛脂。較佳的油添加劑包括C8 -C22 脂肪酸的烷基酯，尤其是C12 -C18 脂肪酸的甲基衍生物，例如月桂酸、棕櫚酸以及油酸的甲基酯（分別為月桂酸甲酯、棕櫚酸甲酯和油酸甲酯）。許多油衍生物獲知於Compendium of Herbicide Adjuvants [除草劑佐劑綱要]，第10版，南伊利諾大學，2010。The composition according to the present invention may include additives including oils of vegetable or animal origin, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additives in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or oils of vegetable origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of vegetable oils, such as methyl derivatives; or oils of animal origin , Such as fish oil or tallow. Preferred oil additives include alkyl esters of C 8 -C 22 fatty acids, especially methyl derivatives of C 12 -C 18 fatty acids, such as methyl esters of lauric acid, palmitic acid and oleic acid (respectively methyl lauric acid Esters, methyl palmitate and methyl oleate). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.
該除草組成物總體上包含按重量計從0.1%至99%、尤其是按重量計從0.1%至95%的具有式 (I) 之化合物和按重量計從1%至99.9%的配製佐劑，該配製佐劑較佳的是包括按重量計從0至25%的表面活性物質。該等本發明組成物總體上包括按重量計從0.1%至99%，尤其是按重量計從0.1%至95%的本發明的化合物以及按重量計從1%至99.9%的配製佐劑，該配製佐劑較佳的是包括按重量計從0至25%的表面活性物質。而商業產品可以較佳的是被配製為濃縮物，最終使用者將通常使用稀釋配製物。The herbicidal composition generally comprises from 0.1% to 99% by weight, especially from 0.1% to 95% by weight of the compound of formula (I) and from 1% to 99.9% by weight of formulated adjuvant The formulation adjuvant preferably includes from 0 to 25% by weight of surface active substance. The compositions of the present invention generally comprise from 0.1% to 99% by weight, especially from 0.1% to 95% by weight of the compound of the present invention, and from 1% to 99.9% by weight of formulated adjuvant, The formulated adjuvant preferably includes from 0 to 25% by weight of surface active substance. While commercial products can preferably be formulated as concentrates, end users will usually use dilute formulations.
施用比率在寬範圍之內變化並且取決於土壤的性質、施用方法、作物植物、待控制的有害生物、主要氣候條件、以及受施用方法、施用時間以及目標作物支配的其他因素。一般來講，可以將化合物以從1 l/ha至2000 l/ha、尤其是從10 l/ha到1000 l/ha的比率施用。 較佳的配製物可以具有以下組成（重量%）： 可乳化的濃縮物： 活性成分： 1%至95%，較佳的是60%至90% 表面活性劑： 1%至30%，較佳的是5%至20% 液體載體： 1%至80%，較佳的是1%至35% 塵劑： 活性成分： 0.1%至10%、較佳的是0.1%至5% 固體載體： 99.9%至90%，較佳的是99.9%至99% 懸浮液濃縮劑： 活性成分： 5%至75%、較佳的是10%至50% 水： 94%至24%、較佳的是88%至30% 表面活性劑： 1%至40%、較佳的是2%至30% 可濕性粉劑： 活性成分： 0.5%至90%、較佳的是1%至80% 表面活性劑： 0.5%至20%，較佳的是1%至15% 固體載體： 5%至95%、較佳的是15%至90% 顆粒劑： 活性成分： 0.1%至30%、較佳的是0.1%至15% 固體載體： 99.5%至70%、較佳的是97%至85%The application rate varies within a wide range and depends on the nature of the soil, application method, crop plants, pests to be controlled, main climatic conditions, and other factors governed by the application method, application time, and target crop. Generally speaking, the compound can be applied at a rate from 1 l/ha to 2000 l/ha, especially from 10 l/ha to 1000 l/ha. A preferred formulation may have the following composition (weight %): Emulsifiable concentrate: Active ingredient: 1% to 95%, preferably 60% to 90% Surfactant: 1% to 30%, preferably 5% to 20% Liquid carrier: 1% to 80%, preferably 1% to 35% Dust agent: Active ingredient: 0.1% to 10%, preferably 0.1% to 5% Solid carrier: 99.9% to 90%, preferably 99.9% to 99% Suspension concentrate: Active ingredient: 5% to 75%, preferably 10% to 50% Water: 94% to 24%, preferably 88% to 30% Surfactant: 1% to 40%, preferably 2% to 30% Wettable powder: Active ingredient: 0.5% to 90%, preferably 1% to 80% Surfactant: 0.5% to 20%, preferably 1% to 15% Solid carrier: 5% to 95%, preferably 15% to 90% Granules: Active ingredient: 0.1% to 30%, preferably 0.1% to 15% Solid carrier: 99.5% to 70%, preferably 97% to 85%
本發明的組成物可以進一步包含至少一種另外的殺有害生物劑。例如，根據本發明的化合物也可以與其他除草劑或植物生長調節劑組合使用。在較佳的實施方式中，該另外的殺有害生物劑係除草劑和/或除草劑安全劑。The composition of the present invention may further comprise at least one additional pesticide. For example, the compounds according to the invention can also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment, the additional pesticidal agent is a herbicide and/or herbicide safener.
因此，具有式 (I) 之化合物可與一種或多種其他除草劑組合使用以提供各種除草混合物。此類混合物的具體實例包括（其中「I」表示具有式 (I) 之化合物）：- I + 乙草胺（acetochlor）；I + 三氟羧草醚（acifluorfen）（包括三氟羧草醚-鈉）；I + 苯草醚（aclonifen）；I + 甲草胺（alachlor）；I + 禾草滅（alloxydim）；I + 莠滅淨（ametryn）；I + 氨唑草酮（amicarbazone）；I + 醯嘧磺隆（amidosulfuron）；I + 環丙嘧啶酸（aminocyclopyrachlor ）；I + 氯氨基吡啶酸（aminopyralid）；I + 殺草強（amitrole）；I + 磺草靈（asulam）；I + 莠去津（atrazine）；I + 苄嘧磺隆（bensulfuron）（包括苄嘧磺隆-甲基）；I + 噻草平（bentazone）；I + 二環吡喃酮（bicyclopyrone）；I + 雙丙氨膦（bilanafos）；I + 治草醚（bifenox）；I + 雙草醚-鈉（bispyribac-sodium）；I + bixlozone；I + 除草定（bromacil）；I + 溴苯腈（bromoxynil）；I + 丁草胺（butachlor）；I + 氟丙嘧草酯（butafenacil）；I + 唑草胺（cafenstrole）；I + 唑酮草酯（carfentrazone）（包括唑酮草酯-乙基）；酯磺草胺酸（cloransulam）（包括酯磺草胺酸-甲基）；I + 氯嘧磺隆（chlorimuron）（包括氯嘧磺隆-乙基）；I + 綠麥隆（chlorotoluron）；I + 醚磺隆（cinosulfuron）；I + 氯磺隆（chlorsulfuron）；I + 環庚草醚（cinmethylin）；I + 氯醯草膦（clacyfos）；I + 烯草酮（clethodim）；I + 炔草酸（clodinafop）（包括炔草酸-炔丙基）；I + 異噁草酮（clomazone）；I + 二氯吡啶酸（clopyralid）；I + 環吡拉尼（cyclopyranil）；I + 環吡瑞莫（cyclopyrimorate）（cyclopyrimorate）；I + 環丙嘧磺隆（cyclosulfamuron）；I + 氰氟草酯（cyhalofop）（包括氰氟草酯-丁基）；I + 2,4-D（包括其膽鹼鹽和2-乙基己酯））；I + 2,4-DB；I + 殺草隆（daimuron）；I + 甜菜安（desmedipham）；I + 麥草畏（dicamba）（包括其鋁、氨基丙基、雙-氨基丙基甲基、膽鹼、二氯丙、二甘醇胺、二甲胺、二甲基銨、鉀鹽和鈉鹽）；I + 禾草靈（diclofop-methyl）；I + 雙氯磺草胺（diclosulam）；I + 吡氟草胺（diflufenican）；I + 野燕枯（difenzoquat）；I + 吡氟草胺（diflufenican）；I + 氟吡草腙（diflufenzopyr）；I + 二甲草胺（dimethachlor）；I + 精二甲吩草胺（dimethenamid-P）；I + 敵草快二溴化物（diquat dibromide）；I + 敵草隆（diuron）；I + 禾草畏（esprocarb）；I + 丁氟消草（ethalfluralin）；I + 乙氧呋草黃（ethofumesate）；I + 噁唑禾草靈（fenoxaprop）（包括精噁唑禾草靈-乙基）；I + 異噁苯碸（fenoxasulfone）；I + 芬奎三酮（fenquinotrione）；I + 四唑醯草胺（fentrazamide）；I + 啶嘧磺隆（flazasulfuron）；I + 雙氟磺草胺（florasulam）；I + 氯氟吡啶酯（florpyrauxifen）；I + 吡氟禾草靈（fluazifop）（包括精吡氟禾草靈-丁基）；I + 氟酮磺隆（flucarbazone）（包括氟酮磺隆-鈉）；；I + 氟噻草胺（flufenacet）；I + 氟節胺（flumetralin）；I + 唑嘧磺草胺（flumetsulam）；I + 丙炔氟草胺（flumioxazin）；I + 氟啶嘧磺隆（flupyrsulfuron）（包括氟啶嘧磺隆-甲基-鈉）；；I + 氟草煙（fluroxypyr）（包括氯氟吡氧乙酸）；；I + 氟噻甲草酯（fluthiacet-methyl）；I + 氟磺胺草醚（fomesafen）；I + 甲醯胺磺隆（foramsulfuron）；I + 草銨膦（glufosinate）（包括其銨鹽）；I + 草甘膦（glyphosate）（包括其聯胺、異丙基銨和鉀鹽）；I + 氟氯吡啶酯（halauxifen）（包括氟氯吡啶酯-甲基）；I + 氯吡嘧磺隆（halosulfuron-methyl）；I + 吡氟氯禾靈（haloxyfop）（包括吡氟氯禾靈-甲基）；I + 環嗪酮（hexazinone）；I + hydantocidin；I + 甲氧咪草煙（imazamox）；I + 甲基咪草煙（imazapic）；I + 滅草煙（imazapyr）；I + 滅草喹（imazaquin）；I + 咪草煙（imazethapyr）；I + 三嗪茚草胺（indaziflam）；I + 碘甲磺隆（iodosulfuron）（包括碘甲磺隆-甲基-鈉）；I + 異歐芬磺隆（iofensulfuron）；I + 異歐芬磺隆-鈉（iofensulfuron-sodium）；I + 碘苯腈（ioxynil）；I + 三唑醯草胺（ipfencarbazone）；I + 異丙隆（isoproturon）；I + 異惡醯草胺（isoxaben）；I + 異噁唑草酮（isoxaflutole）；I + 乳氟禾草靈（lactofen）；I + lancotrione；I + 利穀隆（linuron）；I + MCPA；I + MCPB；I + 高二甲四氯丙酸（mecoprop-P）；I + 苯噻醯草胺（mefenacet）；I + 甲基二磺隆（mesosulfuron）；I + 甲基二磺隆-甲基（mesosulfuron-methyl）；I + 甲基磺草酮（mesotrione）；I + 苯嗪草酮（metamitron）；I + 吡草胺（metazachlor）；I + 異噁噻草醚（methiozolin）；I + 秀穀隆（metobromuron）；I + 異丙甲草胺（metolachlor）；I + 磺草唑胺（metosulam）；I + 甲氧隆（metoxuron）；I + 嗪草酮（metribuzin）；I + 甲磺隆（metsulfuron）；I + 草達滅（molinate）；I + 敵草胺（napropamide）；I + 煙嘧磺隆（nicosulfuron）；I + 達草滅（norflurazon）；I + 嘧苯胺磺隆（orthosulfamuron）；I + 炔惡草酮（oxadiargyl）；I + 噁草酮（oxadiazon）；I + 環氧嘧磺隆（oxasulfuron）；I + 乙氧氟草醚（oxyfluorfen）；I + 二氯化百草枯（paraquat dichloride）；I + 二甲戊樂靈（pendimethalin）；I + 五氟磺草胺（penoxsulam）；I + 苯敵草（phenmedipham）；I + 毒莠定（picloram）；I + 氟吡醯草胺（picolinafen）；I + 唑啉草酯（pinoxaden）；I + 丙草胺（pretilachlor）；I + 氟嘧磺隆-甲基（primisulfuron-methyl）；I + 氨氟樂靈（prodiamine）；I + 撲草淨（prometryn）；I + 毒草胺（propachlor）；I + 敵稗（propanil）；I + 喔草酯（propaquizafop）；I + 苯胺靈（propham）；I + 丙嗪嘧磺隆（propyrisulfuron）、I + 戊炔草胺（propyzamide）；I + 苄草丹（prosulfocarb）；I + 氟磺隆（prosulfuron）；I + 雙唑草腈（pyraclonil）；I + 吡草醚（包括吡草醚-乙基）；I + 磺醯草吡唑（pyrasulfotole）；I + 吡唑特（pyrazolynate）、I + 吡嘧磺隆（pyrazosulfuron-ethyl）；I + 嘧啶肟草醚（pyribenzoxim）；I + 噠草特（pyridate）；I + 環酯草醚（pyriftalid）；I + 吡丙醚（pyrimisulfan）、I + 嘧草硫醚（pyrithiobac-sodium）；I + 吡咯磺隆（pyroxasulfone）；I + 啶磺草胺（pyroxsulam ）；I + 二氯喹啉酸（quinclorac）；I + 氯甲喹啉酸（quinmerac）；I + 喹禾靈（quizalofop）（包括精喹禾靈-乙基）和喹禾糠酯（quizalofop-P-tefuryl））；I + 碸嘧磺隆（rimsulfuron）；I + 苯嘧磺草胺（saflufenacil）；I + 烯禾啶（sethoxydim）；I + 西瑪津（simazine）；I + S-異丙甲草胺（S-metolachlor）；I + 磺草酮（sulcotrione）；I + 甲磺草胺（sulfentrazone）；I + 磺醯磺隆（sulfosulfuron）；I + 特丁噻草隆（tebuthiuron）；I + 特呋三酮（tefuryltrione）；I + 環磺酮（tembotrione）；I + 特丁津（terbuthylazine）；I + 特丁淨（terbutryn）；I + 噻酮磺隆（thiencarbazone）；I + 噻吩磺隆（thifensulfuron）；I + 地芬納噻（tiafenacil）；I + 托比利特（tolpyralate）；I + 苯吡唑草酮（topramezone）；I + 三甲苯草酮（tralkoxydim）；I + 氟酮磺草胺（triafamone）（triafamone）；I + 野麥畏（triallate）；I + 醚苯磺隆（triasulfuron）；I + 苯磺隆（tribenuron）（包括苯磺隆-甲基）；I + 綠草定（triclopyr）；I + 三氟啶磺隆（trifloxysulfuron）（包括三氟啶磺隆-鈉）；I + 三氣草嗦（trifludimoxazin）；I + 氟樂靈（trifluralin）；I + 氟胺磺隆（triflusulfuron）；I + 三氟甲磺隆（tritosulfuron）；I + 4-羥基-1-甲氧基-5-甲基-3-[4-(三氟甲基)-2-吡啶基]咪唑啶-2-酮；I + 4-羥基-1,5-二甲基-3-[4-(三氟甲基)-2-吡啶基]咪唑啶-2-酮；I + 5-乙氧基-4-羥基-1-甲基-3-[4-(三氟甲基)-2-吡啶基]咪唑啶-2-酮；I + 4-羥基-1-甲基-3-[4-(三氟甲基)-2-吡啶基]咪唑啶-2-酮；I + 4-羥基-1,5-二甲基-3-[1-甲基-5-(三氟甲基)吡唑-3-基]咪唑啶-2-酮；I + (4R)1-(5-三級丁基異㗁唑-3-基)-4-乙氧基-5-羥基-3-甲基-咪唑啶-2-酮；I + 3-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]二環[3.2.1]辛烷-2,4-二酮；I + 2-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]-5-甲基-環己烷-1,3-二酮；I + 2-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]環己烷-1,3-二酮；I + 2-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]-5,5-二甲基-環己烷-1,3-二酮；I + 6-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]-2,2,4,4-四甲基-環己烷-1,3,5-三酮；I + 2-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]-5-乙基-環己烷-1,3-二酮；I + 2-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]-4,4,6,6-四甲基-環己烷-1,3-二酮；I + 2-[6-環丙基-2-(3,4-二甲氧基苯基)-3-側氧基-嗒𠯤-4-羰基]-5-甲基-環己烷-1,3-二酮；I + 3-[6-環丙基-2-(3,4-二甲氧基苯基)-3-側氧基-嗒𠯤-4-羰基]二環[3.2.1]辛烷-2,4-二酮；I + 2-[6-環丙基-2-(3,4-二甲氧基苯基)-3-側氧基-嗒𠯤-4-羰基]-5,5-二甲基-環己烷-1,3-二酮；I + 6-[6-環丙基-2-(3,4-二甲氧基苯基)-3-側氧基-嗒𠯤-4-羰基]-2,2,4,4-四甲基-環己烷-1,3,5-三酮；I + 2-[6-環丙基-2-(3,4-二甲氧基苯基)-3-側氧基-嗒𠯤-4-羰基]環己烷-1,3-二酮；I + 4-[2-(3,4-二甲氧基苯基)-6-甲基-3-側氧基-嗒𠯤-4-羰基]-2,2,6,6-四甲基-四氫哌喃-3,5-二酮和I + 4-[6-環丙基-2-(3,4-二甲氧基苯基)-3-側氧基-嗒𠯤-4-羰基]-2,2,6,6-四甲基-四氫哌喃-3,5-二酮。Therefore, the compound of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures. Specific examples of such mixtures include (wherein "I" represents a compound of formula (I)):-I + acetochlor; I + acifluorfen (including acifluorfen- Sodium); I + aclonifen (aclonifen); I + alachlor; I + alloxydim; I + ametryn; I + amicarbazone; I + Amidosulfuron (amidosulfuron); I + aminocyclopyrachlor; I + aminopyralid; I + amitrole; I + asulam; I + atrazine Atrazine; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bialanin Phosphine (bilanafos); I + bifenox; I + bispyribac-sodium; I + bixlozone; I + bromacil; I + bromoxynil; I + Butachlor; I + butafenacil; I + cafenstrole; I + carfentrazone (including carfentrazone-ethyl); Cloransulam (including acesulfame-methyl); I + chlorimuron (including chlorimuron-ethyl); I + chlorotoluron; I + chlorotoluron Cinosulfuron; I + chlorsulfuron; I + cinmethylin; I + clacyfos; I + clacyfos; I + clacyfos; I + clodinafop (Including propargyl-propargyl); I + clomazone; I + clopyralid; I + cyclopyranil; I + cyclopyrimorate ( cyclopyrimorate); I + cyclosulfamuron; I + cyhalofop (including cyhalofop-butyl) ; I + 2,4-D (including its choline salt and 2-ethylhexyl ester)); I + 2,4-DB; I + daimuron; I + desmedipham; I + Dicamba (dicamba) (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium salt and sodium salt) ; I + diclofop-methyl; I + diclofop-methyl; I + diflufenican; I + difenzoquat; I + diflufenican ); I + diflufenzopyr; I + dimethachlor; I + dimethenamid-P; I + diquat dibromide; I + Diuron (diuron); I + esprocarb; I + ethalfluralin; I + ethofumesate; I + fenoxaprop (including Fenoxaprop-ethyl); I + fenoxasulfone; I + fenquinotrione; I + fentrazamide; I + flazasulfuron ); I + florasulam (florasulam); I + florpyrauxifen; I + fluazifop (including fluazifop-butyl); I + fluoroketone Flucarbazone (including flumetsulam-sodium);; I + flufenacet; I + flumetralin; I + flumetsulam; I + propyne Flumioxazin (flumioxazin); I + flupyrsulfuron (including flupyrsulfuron-methyl-sodium); I + fluroxypyr (including fluroxypyr); I + fluthiacet-methyl; I + fomesafen; I + foramsulfuron; I + glufosinate (including its ammonium salt); I + Glyphosate (including its hydrazine, isopropylammonium and potassium salt); I + fluclopyridine ester (ha lauxifen) (including fluclopyr-methyl); I + halosulfuron-methyl; I + haloxyfop (including haloxyfop-methyl); I + Hexazinone; I + hydantocidin; I + imazamox; I + imazapic; I + imazapyr; I + imazaquin ; I + imazethapyr; I + indaziflam; I + iodosulfuron (including iodosulfuron-methyl-sodium); I + isofensulfuron (Iofensulfuron); I + isofensulfuron-sodium; I + ioxynil; I + ipfencarbazone; I + isoproturon; I + Isoxaben; I + isoxaflutole; I + lactofen; I + lancotrione; I + linuron; I + MCPA; I + MCPB; I + mecoprop-P; I + mefenacet; I + mesosulfuron; I + mesosulfuron-methyl (mesosulfuron) -methyl); I + mesotrione; I + metamitron; I + metazachlor; I + methiozolin; I + Xiugulong (Metobromuron); I + metolachlor; I + metolachlor; I + metoxuron; I + metribuzin; I + metsulfuron ); I + molinate; I + napropamide; I + nicosulfuron; I + norflurazon; I + orthosulfamuron; I + Oxadiargyl; I + oxadiazon; I + oxasulfuron ron); I + oxyfluorfen; I + paraquat dichloride (paraquat dichloride); I + pendimethalin (pendimethalin); I + penoxsulam (penoxsulam); I + Phenmedipham; I + picloram; I + picolinafen; I + pinoxaden; I + pretilachlor; I + flumesulfuron Primisulfuron-methyl (primisulfuron-methyl); I + prodiamine; I + prometryn; I + propachlor; I + propanil; I + propanil (Propaquizafop); I + propham; I + propyrisulfuron, I + propyzamide; I + prosulfocarb; I + prosulfuron ; I + pyraclonil (pyraclonil); I + pyraclonil (including pyrachlor-ethyl); I + pyrasulfotole; I + pyrazolynate, I + pyrazolone Pyrazosulfuron-ethyl; I + pyribenzoxim; I + pyridate; I + pyriftalid; I + pyrimisulfan, I + pyribenzoxim Sulfide (pyrithiobac-sodium); I + pyroxasulfone; I + pyroxsulam; I + quinclorac; I + quinmerac; I + Quizalofop (including quizalofop-ethyl) and quizalofop-P-tefuryl); I + rimsulfuron (rimsulfuron); I + saflufenacil (saflufenacil) ; I + sethoxydim (sethoxydim); I + simazine (simazine); I + S-metolachlor (S-metolachlor); I + sulcotrione (sulcotrione); I + sulfentrazone ( sulfentrazone); I + sulfentrazone (s ulfosulfuron; I + tebuthiuron; I + tefuryltrione; I + tembotrione; I + terbuthylazine; I + terbutryn ; I + thiencarbazone; I + thifensulfuron; I + tiafenacil; I + tolpyralate; I + topramezone ; I + tralkoxydim; I + triafamone (triafamone); I + triallate; I + triasulfuron (triasulfuron); I + triasulfuron ( tribenuron (including tribenuron-methyl); I + trifloxysulfuron (trifloxysulfuron) (including trifloxysulfuron-sodium); I + trifludimoxazin ); I + trifluralin (trifluralin); I + triflusulfuron (triflusulfuron); I + tritosulfuron (tritosulfuron); I + 4-hydroxy-1-methoxy-5-methyl-3 -[4-(Trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2 -Pyridyl]imidazolidin-2-one; I + 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2- Ketone; I + 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I + 4-hydroxy-1,5-dimethyl -3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one; I + (4R)1-(5-tertiary butylisoxazole-3 -Yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one; I + 3-[2-(3,4-dimethoxyphenyl)-6-methyl -3-Pendant oxy-ta𠯤-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[2-(3,4-dimethoxyphenyl) -6-Methyl-3-pendant oxy-paza-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethyl Oxyphenyl)-6-methyl-3- pendant oxy-paza-4-carbonyl]cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethoxy Phenyl)-6-methyl-3-oxo -Da 𠯤-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; I + 6-[2-(3,4-dimethoxyphenyl)-6- Methyl-3-pendant oxy-ta 𠯤-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I + 2-[2-( 3,4-Dimethoxyphenyl)-6-methyl-3-oxo-taza-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione; I + 2 -[2-(3,4-Dimethoxyphenyl)-6-methyl-3- pendant oxy-ta𠯤-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexyl Alkyl-1,3-dione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3- pendant oxy-ta𠯤-4-carbonyl]-5 -Methyl-cyclohexane-1,3-dione; I + 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3- pendant oxy-pah 𠯤- 4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-side Oxy-ta 𠯤-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; I + 6-[6-cyclopropyl-2-(3,4-dimethyl (Oxyphenyl)-3-Pendant oxy-ta 𠯤-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I + 2-[ 6-Cyclopropyl-2-(3,4-Dimethoxyphenyl)-3-Pendant oxy-ta 𠯤-4-carbonyl]cyclohexane-1,3-dione; I + 4-[ 2-(3,4-Dimethoxyphenyl)-6-methyl-3-oxo-pano-4-carbonyl)-2,2,6,6-tetramethyl-tetrahydropiperan -3,5-dione and I + 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-pendant oxy-ta𠯤-4-carbonyl]-2, 2,6,6-Tetramethyl-tetrahydropiperan-3,5-dione.
具有式 (I) 之化合物的混合配伍物還可以呈酯或鹽的形式，例如在以下文獻中所提到的：The Pesticide Manual, Fourteenth Edition, British Crop Protection Council [《殺有害生物劑手冊》，第十四版，英國作物保護委員會], 2006。The mixed compatibility of the compound of formula (I) can also be in the form of ester or salt, for example, as mentioned in the following documents: The Pesticide Manual, Fourteenth Edition, British Crop Protection Council ["Pesticide Manual", Fourteenth edition, British Crop Protection Council], 2006.
具有式 (I) 之化合物還可以在與其他農用化學品（如殺真菌劑、殺線蟲劑或殺昆蟲劑）的混合物中使用，該等農用化學品的實例在殺有害生物劑手冊中給出。The compounds of formula (I) can also be used in mixtures with other agrochemicals (such as fungicides, nematicides or insecticides). Examples of such agrochemicals are given in the Pesticide Manual .
具有式 (I) 之化合物與混合配伍物的混合比較佳的是從1 : 100至1000 : 1。The mixing ratio of the compound of formula (I) and the mixed compatibility is preferably from 1:100 to 1000:1.
該等混合物可以有利地用於以上提到的該等配製物中（在這種情況下「活性成分」涉及具有式 (I) 之化合物與混合配伍物的對應混合物）。These mixtures can be advantageously used in the above-mentioned formulations (in this case the "active ingredient" refers to the corresponding mixture of the compound of formula (I) and the mixed compatibility).
本發明的具有式 (I) 之化合物也可以與除草劑安全劑組合。較佳的組合（其中「I」表示具有式 (I) 之化合物）包括：-I + 解草嗪（benoxacor）；I + 解草酯（cloquintocet）（包括解草喹（cloquintocet-mexyl））；I + 環丙磺醯胺（cyprosulfamide）；I + 二氯丙烯胺（dichlormid）；I + 解草唑（fenchlorazole）（包括解草唑乙酯）；I + 解草啶（fenclorim）； I + 氟草肟（fluxofenim）；I+ 解草惡唑（furilazole）、I + 雙苯㗁唑酸（isoxadifen）（包括雙苯㗁唑酸-乙基）；I + 吡唑解草酸（mefenpyr）（包括吡唑解草酯（mefenpyr-diethyl））；I + metcamifen；I+N-(2-甲氧基苯甲醯基)-4-[(甲基胺基羰基)胺基]苯磺醯胺和I+解草腈（oxabetrinil）。The compound of formula (I) of the present invention can also be combined with herbicide safeners. A preferred combination (wherein "I" represents a compound of formula (I)) includes: -I + benoxacor; I + cloquintocet (including cloquintocet-mexyl); I + cyprosulfamide (cyprosulfamide); I + dichlormid; I + fenchlorazole (including fenchlorazole); I + fenclorim; I + fluorine Fluxofenim; I+ furilazole, I + isoxadifen (including isoxadifen-ethyl); I + mefenpyr (including pyrazole) Mefenpyr-diethyl); I + metcamifen; I+N-(2-methoxybenzyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide and I+ Oxabetrinil (oxabetrinil).
特別較佳的是具有式 (I) 之化合物與環丙磺醯胺、雙苯㗁唑酸（包括雙苯㗁唑酸-乙基）、解草酯（包括解草喹）和/或N-(2-甲氧基苯甲醯基)-4-[(甲基-胺基羰基)胺基]苯磺醯胺的混合物。Particularly preferred are the compounds of formula (I) with cyprofenamide, benzoic acid (including benzoic acid-ethyl), hydrochloride (including hydrochloric acid) and/or N- A mixture of (2-methoxybenzyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.
具有式 (I) 之化合物的該等安全劑還可以處於酯或鹽的形式，例如像在《殺有害生物劑手冊》（第14版（BCPC），2006）中所提及的。提及解毒喹還適用於一種鋰、鈉、鉀、鈣、鎂、鋁、鐵、銨、季銨、鋶或其鏻鹽（如在WO 02/34048中揭露的），並且對解草唑乙酯（fenchlorazole-ethyl）的提及還適用於解草唑（fenchlorazole），等等。The safeners with compounds of formula (I) can also be in the form of esters or salts, as mentioned in the "Handbook of Pesticides" (14th edition (BCPC), 2006), for example. It is mentioned that Jieduquine is also applicable to a kind of lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, amphetamine or its phosphonium salt (as disclosed in WO 02/34048), and is suitable for The mention of fenchlorazole-ethyl also applies to fenchlorazole, etc.
較佳的是，具有式 (I) 之化合物與安全劑的混合比係從100 : 1至1 : 10，尤其是從20 : 1至1 : 1。Preferably, the mixing ratio of the compound of formula (I) and the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.
該等混合物可有利地用於以上提到的配製物中（在這種情況下「活性成分」涉及具有式 (I) 之化合物與安全劑的對應混合物）。These mixtures can be advantageously used in the formulations mentioned above (in this case the "active ingredient" refers to the corresponding mixture of the compound of formula (I) and the safener).
本發明的具有式 (I) 之化合物作為除草劑係有用的。因此，本發明還包括用於控制不想要的植物的方法，包括向該植物或包含它們的場所施用有效量的本發明化合物或含有該化合物的除草組成物。‘控制’意指殺死、減少或延遲生長或防止或減少發芽。通常有待控制的植物係不想要的植物（雜草）。‘場所’意指其中植物正生長或將生長的區域。The compounds of the present invention having the formula (I) are useful as herbicides. Therefore, the present invention also includes a method for controlling unwanted plants, including applying an effective amount of the compound of the present invention or a herbicidal composition containing the compound to the plant or a locus containing them. ‘Control’ means killing, reducing or delaying growth or preventing or reducing germination. Usually there are unwanted plants (weeds) in the plant line to be controlled. A'location' means an area where plants are growing or will grow.
具有式 (I) 之化合物的施用比率可以在寬的限度內變化並且取決於土壤的性質、施用的方法（出苗前；出苗後；施用於種子溝；免耕法施用等）、作物植物、待控制的一種或多種雜草、盛行的氣候條件和其他受施用方法、施用時間和目標作物支配的因素。根據本發明的具有式 (I) 之化合物通常以從10 g/ha至2000 g/ha，尤其是從50 g/ha到1000 g/ha的比率施用。The application rate of the compound of formula (I) can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence; post-emergence; application in the seed furrow; no-till application, etc.), crop plants, One or more weeds to be controlled, prevailing climatic conditions and other factors governed by application method, application time and target crop. The compounds of formula (I) according to the invention are usually applied at a rate of from 10 g/ha to 2000 g/ha, especially from 50 g/ha to 1000 g/ha.
通常藉由噴灑該組成物進行施用，典型地是藉由用於大面積的裝在拖拉機上的噴灑機，但是還可以使用其他方法如撒粉（針對粉末）、滴加或者浸濕。It is usually applied by spraying the composition, typically by a sprayer installed on a tractor for a large area, but other methods such as dusting (for powder), dripping or soaking can also be used.
可以使用根據本發明的組成物的有用植物，包括作物如穀物，例如大麥和小麥、棉花、油菜籽油菜、向日葵、玉米、稻、大豆、甜菜、甘蔗和草皮。Useful plants for which the composition according to the present invention can be used include crops such as grains such as barley and wheat, cotton, rapeseed rape, sunflower, corn, rice, soybean, sugar beet, sugar cane, and turf.
作物植物還可以包括樹，如果樹、棕櫚樹、椰子樹或其他堅果。還包括藤本植物（如葡萄）、灌木果樹、果實植物和蔬菜。Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. It also includes vines (such as grapes), shrub fruit trees, fruit plants and vegetables.
作物應被理解為還包括藉由常規的育種方法或藉由基因工程已經賦予對除草劑或多種類別的除草劑（例如ALS-抑制劑、GS-抑制劑、EPSPS-抑制劑、PPO-抑制劑、ACC酶-抑制劑和HPPD-抑制劑）的耐受性的那些作物。藉由常規育種方法已經賦予其對咪唑啉酮（例如，甲氧咪草煙）的耐受性的作物的實例係Clearfield®夏季油菜（卡諾拉（canola））。藉由基因工程方法而賦予對除草劑的耐受性的作物的實例包括例如草甘膦和草銨膦抗性的玉米品種，該玉米品種在RoundupReady®和LibertyLink®商標名下是可商購的。Crops should be understood to also include herbicides or herbicides of various classes that have been conferred by conventional breeding methods or by genetic engineering (such as ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors , ACC enzyme-inhibitors and HPPD-inhibitors). An example of a crop that has been given tolerance to imidazolinones (for example, imazamox) by conventional breeding methods is Clearfield® summer rape (canola). Examples of crops that are given herbicide tolerance by genetic engineering methods include, for example, glyphosate and glufosinate-resistant corn varieties, which are commercially available under the trade names RoundupReady® and LibertyLink® .
農作物還應理解為藉由基因工程方法已經賦予其對有害昆蟲有抗性的那些農作物，例如Bt玉米（對歐洲玉米螟有抗性）、Bt棉花（對棉鈴象鼻蟲有抗性）和還有Bt馬鈴薯（對科羅拉多甲蟲有抗性）。Bt玉米的實例係NK®的Bt 176玉米雜交體（先正達種子公司（Syngenta Seeds））。Bt毒素係由蘇蕓金芽孢桿菌土壤細菌天然形成的蛋白質。毒素或能夠合成此類毒素的轉基因植物的實例被描述在EP-A-451 878、EP-A-374 753、WO 93/07278、WO 95/34656、WO 03/052073和EP-A-427 529中。包含一個或多個編碼殺昆蟲劑抗性和表現一種或多種毒素的基因的轉基因植物的實例係KnockOut®（玉米）、Yield Gard®（玉米）、NuCOTIN33B®（棉花）、Bollgard®（棉花）、NewLeaf®（馬鈴薯）、NatureGard®和Protexcta®。植物作物或其種子材料均可以是抗除草劑的並且同時係抗昆蟲攝食的（「疊加的」轉基因結果）。例如，種子可以具有表現殺昆蟲的Cry3蛋白的能力，而同時對草甘膦係耐受的。Crops should also be understood as those crops that have been conferred resistance to harmful insects by genetic engineering methods, such as Bt corn (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also There are Bt potatoes (resistant to Colorado beetles). An example of Bt corn is NK®'s Bt 176 corn hybrid (Syngenta Seeds). Bt toxin is a protein naturally formed by Bacillus thuringiensis soil bacteria. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529 in. Examples of transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Plant crops or their seed materials can both be herbicide-resistant and also insect-resistant ("stacked" transgenic results). For example, seeds can have the ability to express the insecticidal Cry3 protein, while at the same time being tolerant to glyphosate lines.
作物還應被理解為包括藉由常規的育種或基因工程的方法獲得並且含有所謂的輸出型（output）性狀（例如改進的儲存能力、更高的營養價值和改進的香味）的那些。Crops should also be understood to include those obtained by conventional breeding or genetic engineering methods and containing so-called output traits (such as improved storage capacity, higher nutritional value, and improved flavor).
其他有用的植物包括例如在高爾夫球場、草地、公園和路旁的或者商業上種植用於草地的草皮草，和觀賞植物，如花卉或者灌木。Other useful plants include, for example, turf grasses that are grown on golf courses, grasslands, parks, and roadsides or commercially grown for grass, and ornamental plants such as flowers or shrubs.
本發明的具有式 (I) 之化合物和組成物通常可以用於控制多種單子葉和雙子葉雜草物種。典型地可以被控制的單子葉物種的實例包括大穗看麥娘（Alopecurus myosuroides ）、野燕麥（Avena fatua ）、車前臂形草（Brachiaria plantaginea ）、旱雀麥（Bromus tectorum ）、油莎草（Cyperus esculentus ）、馬唐（Digitaria sanguinalis ）、稗草（Echinochloa crus-galli ）、多年生黑麥草（Lolium perenn ）、多花黑麥草（Lolium multiflorum ）、黍稷（Panicum miliaceum ）、一年生早熟禾（Poa annua ）、狗尾草（Setaria viridis ）、大狗尾草（Setaria faberi ）和兩色蜀黍（Sorghum bicolor ）。可以被控制的雙子葉物種的實例包括：苘麻（Abutilon theophrasti ）、反枝莧（Amaranthus retroflexus ）、鬼針草（Bidens pilosa ）、藜草（Chenopodium album ）、白苞猩猩草（Euphorbia heterophylla ）、豬殃殃（Galium aparine ）、牽牛花（Ipomoea hederacea ）、地膚（Kochia scoparia ）、卷莖蓼（Polygonum convolvulus ）、刺金午時花（Sida spinosa ）、新疆野生油菜（Sinapis arvensis, ）、龍葵（Solanum nigrum ）、繁縷（Stellaria media ）、波斯婆婆納（Veronica persica ）和蒼耳（Xanthium strumarium ）。The compounds and compositions of the present invention having the formula (I) can generally be used to control a variety of monocotyledonous and dicotyledonous weed species. Examples of monocot species that can be typically controlled include Alopecurus myosuroides , Avena fatua , Brachiaria plantaginea , Bromus tectorum , and Sedge Cyperus esculentus), crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crus-galli), perennial ryegrass (Lolium perenn), Italian ryegrass (Lolium multiflorum), Shuji (Panicum miliaceum), annual bluegrass (Poa annua ), Setaria viridis , Setaria faberi , and Sorghum bicolor ( Sorghum bicolor ). Examples of dicot species that can be controlled include: Abutilon theophrasti , Amaranthus retroflexus , Bidens pilosa , Chenopodium album , Euphorbia heterophylla , Euphorbia heterophylla , Galium aparine , morning glory ( Ipomoea hederacea ), Kochia scoparia , Polygonum convolvulus , Sida spinosa , Xinjiang wild rapeseed ( Sinapis arvensis, ), nightshade ( Solanum nigrum ), Stellaria media ( Stellaria media ), Persian mother-in-law ( Veronica persica ) and Xanthium strumarium ( Xanthium strumarium ).
具有式 (I) 之化合物也可用於作物收穫前乾燥，例如但不限於馬鈴薯、大豆、向日葵和棉花。收穫前乾燥用於乾燥作物葉片，而不會對作物本身造成顯著損害，以幫助收穫。Compounds of formula (I) can also be used to dry crops before harvest, such as but not limited to potatoes, soybeans, sunflowers and cotton. Drying before harvest is used to dry crop leaves without causing significant damage to the crop itself to help harvest.
本發明的化合物/組成物特別可用於非選擇性燃盡（burn-down）應用，並且因此也可用於控制自生自長（volunteer）或逃逸作物（escape crop）植物。The compounds/compositions of the present invention are particularly useful in non-selective burn-down applications, and therefore can also be used to control volunteers or escape crop plants.
現在將藉由舉例更詳細地說明本發明的不同方面和實施方式。應理解，在不背離本發明範圍的情況下，可以對細節做出修改。實施例
以下實施例用來說明但不限制本發明。配製物實施例
將該組合與該等佐劑充分混合並且將混合物在適當的研磨機中充分研磨，從而獲得了可以用水稀釋而給出所希望的濃度的懸浮液的可濕性粉劑。
在植物保護中可以使用的具有任何所要求的稀釋的乳液可以藉由用水稀釋從這種濃縮物中獲得。
藉由將該組合與載體混合並且將混合物在適當的研磨機中研磨而獲得即用型塵劑。
將該組合與該等佐劑混合並且研磨，並且將混合物用水濕潤。將混合物擠出並且然後在空氣流中乾燥。
將這種精細研磨的組合在混合器中均勻地施用於用聚乙二醇濕潤的高嶺土中。以此方式獲得無塵的包衣的顆粒劑。懸浮液濃縮物
將精細地研磨的組合與佐劑緊密地混合，得到懸浮液濃縮物，從該懸浮液濃縮液可以藉由用水稀釋獲得任何所希望的稀釋度的懸浮液。緩釋的膠囊懸浮液 The finely ground combination is intimately mixed with the adjuvant to obtain a suspension concentrate from which a suspension of any desired dilution can be obtained by diluting with water. Sustained release capsule suspension
將28份的組合與2份的芳香族溶劑以及7份的甲苯二異氰酸酯/聚甲烯-聚苯基異氰酸酯-混合物（8 : 1）進行混合。將此混合物在1.2份的聚乙烯醇、0.05份的消泡劑以及51.6份的水的混合物中進行乳化直至達到所希望的粒度。向此乳液中添加在5.3份的水中的2.8份的1,6-己二胺混合物。將混合物攪拌直至聚合反應完成。Mix 28 parts of the combination with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of antifoaming agent, and 51.6 parts of water until the desired particle size was reached. To this emulsion was added 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.
將獲得的膠囊懸浮液藉由添加0.25份的增稠劑以及3份的分散劑進行穩定。該膠囊懸浮液配製物含有28%的活性成分。介質膠囊的直徑係8-15微米。The obtained capsule suspension was stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsule is 8-15 microns.
將所得配製物作為適用於此目的裝置中的水性懸浮液施用到種子上。縮寫清單： Boc = 三級丁氧基羰基 br = 寬峰 CDCl3 = 氯仿-d CD3 OD = 甲醇-d °C = 攝氏度 D2 O = 水-d DCM = 二氯甲烷 d = 二重峰 dd = 雙二重峰 dt = 雙三重峰 DMSO = 二甲基亞碸 EtOAc = 乙酸乙酯 h = 小時 HCl = 鹽酸 HPLC = 高效液相層析法（下面給出了用於HPLC的裝置和方法的描述） m = 多重峰 M = 體積莫耳濃度 min = 分鐘 MHz = 百萬赫茲 mL = 毫升 mp = 熔點 ppm = 百萬分率 q = 四重峰 quin = 五重峰 rt = 室溫 s = 單峰 t = 三重峰 THF = 四氫呋喃 LC/MS = 液相層析質譜法製備型逆相 HPLC 方法： The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose. List of abbreviations: Boc = tertiary butoxycarbonyl br = broad peak CDCl 3 = chloroform-d CD 3 OD = methanol-d °C = degrees Celsius D 2 O = water-d DCM = dichloromethane d = doublet dd = Double doublet dt = double triplet DMSO = dimethyl sulfide EtOAc = ethyl acetate h = hour HCl = hydrochloric acid HPLC = high performance liquid chromatography (the description of the device and method used for HPLC is given below ) M = multiplet M = volume molar concentration min = minutes MHz = megahertz mL = milliliters mp = melting point ppm = parts per million q = quartet quin = quintet rt = room temperature s = singlet t = triplet THF = tetrahydrofuran LC / MS = preparative reverse-phase liquid chromatography mass spectrometry HPLC method:
將化合物在Waters FractionLynx Autopurification系統上使用ES+/ES-藉由質量定向的製備型HPLC純化，該系統包括具有2545梯度泵的2767注射器/收集器、兩個515等度泵、SFO、2998光電二極體陣列（波長範圍（nm）：210至400）、2424 ELSD和QDa質譜儀。Waters Atlantis T3 5微米19 × 10 mm保護管柱與Waters Atlantis T3 OBD，5微米30 × 100 mm製備管柱一起使用。離子化方法： 電灑正和負：錐孔（V）20.00，源溫度（°C）120，錐孔氣流（L/Hr.）50The compounds were purified by mass-oriented preparative HPLC using ES+/ES- on the Waters FractionLynx Autopurification system, which included a 2767 syringe/collector with 2545 gradient pump, two 515 isocratic pumps, SFO, 2998 photodiode Volume array (wavelength range (nm): 210 to 400), 2424 ELSD and QDa mass spectrometer. Waters Atlantis T3 5 micron 19 × 10 mm guard column is used with Waters Atlantis T3 OBD, 5 micron 30 × 100 mm preparative column. Ionization method: electrospray positive and negative: cone hole (V) 20.00, source temperature (°C) 120, cone air flow (L/Hr.) 50
質量範圍（Da）：正100至800，負115至800。
根據以下梯度表，利用11.4分鐘執行時間來進行製備型HPLC（不使用在管柱稀釋，用管柱選擇器繞開）：
在室溫下將2-胺基苯硫酚（0.1 g）和嗒𠯤-4-甲醛（0.1 g）在二甲基亞碸（2 mL）中的溶液攪拌15小時。將反應混合物濃縮並藉由製備型逆相HPLC純化，以得到呈奶油色固體的2-嗒𠯤-4-基-1,3-苯并噻唑。1 H NMR (400MHz, CD3 OD) 9.91 (br s, 1H), 9.41 (br d, 1H), 8.38 - 8.32 (m, 1H), 8.19 - 8.11 (m, 2H), 7.66 - 7.54 (m, 2H) 步驟2：2-[4-(1,3-苯并噻唑-2-基)嗒𠯤-1-鎓-1-基]乙磺酸鹽A1的製備Stir a solution of 2-aminothiophenol (0.1 g) and 4-carbaldehyde (0.1 g) in dimethyl sulfide (2 mL) at room temperature for 15 hours. The reaction mixture was concentrated and purified by preparative reverse phase HPLC to obtain 2-taza-4-yl-1,3-benzothiazole as a cream-colored solid. 1 H NMR (400MHz, CD 3 OD) 9.91 (br s, 1H), 9.41 (br d, 1H), 8.38-8.32 (m, 1H), 8.19-8.11 (m, 2H), 7.66-7.54 (m, 2H) Step 2: Preparation of 2-[4-(1,3-benzothiazol-2-yl)paza-1-on-1-yl]ethanesulfonate A1
向2-嗒𠯤-4-基-1,3-苯并噻唑（0.20 g，0.93 毫莫耳）在水（2 mL）中的溶液中添加2-溴乙烷磺酸鈉（0.24 g，1.12 毫莫耳），並將反應混合物在100°C下加熱48小時。真空濃縮後，將粗產物藉由製備型逆相HPLC純化，以得到呈黃色固體的2-[4-(1,3-苯并噻唑-2-基)嗒𠯤-1-鎓-1-基]乙磺酸鹽A1。1
H NMR (400 MHz, D2
O) 9.94 - 10.12 (m, 1H), 9.74 - 9.86 (m, 1H), 8.87 - 9.02 (m, 1H), 8.01 - 8.26 (m, 2H), 7.49 - 7.75 (m, 2H), 5.13 - 5.28 (m, 1H), 5.13 - 5.30 (m, 1H), 3.61 - 3.79 (m, 2H)實施例 2 ： 3-(4-(1, 3- 苯并㗁唑 -2- 基 ) 嗒 𠯤 -1- 鎓 -1- 基 ) 丙烷 -1- 磺酸鹽 A2 的製備 
將2-胺基苯酚（0.5 g）和嗒𠯤-4-甲醛（0.5 g）在乙酸（2 mL）中的溶液在100°C下攪拌25小時。將反應冷卻至室溫、濃縮並藉由矽膠管柱層析純化，以得到呈米色固體的2-嗒𠯤-4-基-1,3-苯并㗁唑。1 H NMR (400MHz, CD3 OD) 9.95 - 9.87 (m, 1H), 9.44 (dd, 1H), 8.39 (dd, 1H), 7.85 (dd, 1H), 7.80 - 7.72 (m, 1H), 7.57 - 7.44 (m, 2H) 步驟2：3-[4-(1,3-苯并㗁唑-2-基)嗒𠯤-1-鎓-1-基]丙烷-1-磺酸鹽A2的製備A solution of 2-aminophenol (0.5 g) and 4-carbaldehyde (0.5 g) in acetic acid (2 mL) was stirred at 100°C for 25 hours. The reaction was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 2-tazo-4-yl-1,3-benzoxazole as a beige solid. 1 H NMR (400MHz, CD 3 OD) 9.95-9.87 (m, 1H), 9.44 (dd, 1H), 8.39 (dd, 1H), 7.85 (dd, 1H), 7.80-7.72 (m, 1H), 7.57 -7.44 (m, 2H) Step 2: Preparation of 3-[4-(1,3-benzoxazol-2-yl)paza-1-on-1-yl]propane-1-sulfonate A2
向2-嗒𠯤-4-基-1,3-苯并㗁唑（0.12 g）在二㗁𠮿（2.4 mL）中的溶液中添加氧硫雜環戊烷2,2-二氧化物（0.09 g）並且將反應混合物在100°C下加熱24小時。將所得沈澱物過濾並用丙酮洗滌。將粗混合物藉由製備型逆相HPLC純化，以得到呈黃色固體的3-[4-(1,3-苯并㗁唑-2-基)嗒𠯤-1-鎓-1-基]丙烷-1-磺酸鹽。1
H NMR (400 MHz, D2
O) 9.97 - 10.14 (m, 1H), 9.84 (d, 1H), 9.01 - 9.17 (m, 1H), 7.82 - 7.97 (m, 1H), 7.77 (d, 1H), 7.38 - 7.65 (m, 2H), 4.91 - 5.13 (m, 2H) 2.91 - 3.12 (m, 2H), 2.38 - 2.65 (m, 2H)實施例 3 ： 2-(4- 喹㗁啉 -2- 基嗒 𠯤 -1- 鎓 -1 基 ) 乙烷磺酸鹽 A3 的製備 
在-78°C，在氮氣下，向二異丙基胺基鋰的溶液（四氫呋喃中的1 M溶液，125 mL）中滴加嗒𠯤（10 g）和三正丁基氯化錫（44.6 g）在THF（100 mL）中的溶液。將反應混合物在-78°C下攪拌1小時。將反應混合物加溫至室溫並用飽和水性氯化銨（100 mL）淬滅並用乙酸乙酯（3 × 150 mL）萃取。將有機層經硫酸鈉乾燥，濃縮並藉由二氧化矽層析法純化（用在己烷中的30%乙酸乙酯洗提），以得到呈淡棕色液體的三丁基(嗒𠯤-4-基)錫烷。1
H NMR (400MHz, CDCl3
) 9.17 (t, 1H) 9.02 (dd, 1H) 7.54 (dd, 1H) 1.57-1.49 (m, 6H) 1.37-1.29 (m, 6H) 1.19-1.13 (m, 6H) 0.92-0.86 (m, 9H)
步驟2：2-嗒𠯤-4-基喹㗁啉的製備
將三丁基(嗒𠯤-4-基)錫烷（2.69 g）、2-氯喹㗁啉（1 g）和四(三苯基膦)鈀(0)（0.72 g）在1,4-二㗁𠮿（30 mL）中的混合物在氮氣氣氛下在140°C下在微波輻射下加熱1小時。將反應混合物冷卻至室溫、濃縮並藉由矽膠管柱層析純化，以得到呈固體的2-嗒𠯤-4-基喹㗁啉。1 H NMR (400MHz, CDCl3 ) 10.06 (dd, 1H), 9.41 - 9.47 (m, 2H), 8.27 (dd, 1H), 8.17 - 8.25 (m, 2H), 7.85 - 7.93 (m, 2H) 步驟3：2-(4-喹㗁啉-2-基嗒𠯤-1-鎓-1-基)乙烷磺酸鹽A3的製備Combine tributyl(tada-4-yl)stannane (2.69 g), 2-chloroquinoline (1 g) and tetrakis(triphenylphosphine)palladium(0)(0.72 g) in 1,4-di The mixture in 㗁𠮿 (30 mL) was heated under microwave radiation at 140°C for 1 hour under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 2-daza-4-ylquinoline as a solid. 1 H NMR (400MHz, CDCl 3 ) 10.06 (dd, 1H), 9.41-9.47 (m, 2H), 8.27 (dd, 1H), 8.17-8.25 (m, 2H), 7.85-7.93 (m, 2H) step 3: Preparation of 2-(4-quinoline-2-ylta-1-ium-1-yl)ethanesulfonate A3
將2-嗒𠯤-4-基喹㗁啉（0.5 g）、2-溴乙烷磺酸鈉（0.6 g）和水（7.20 mL）的混合物在100°C下加熱17小時。將反應混合物冷卻至室溫並且藉由製備型逆相HPLC純化，以得到呈黃色固體的2-(5-喹㗁啉-2-基嗒𠯤-1-鎓-1-基)乙烷磺酸鹽。1
H NMR (400MHz, DMSO-d6
) 10.42 - 10.47 (m, 1H), 10.13 (d, 1H), 9.94 - 9.99 (m, 1H), 9.48 (dd, 1H), 8.23 - 8.23 (m, 2H), 8.01 - 8.12 (m, 2H), 5.16 (t, 2H), 3.25 (t, 2H)實施例 4 ： 3-(4- 喹㗁啉 -2- 基嗒 𠯤 -1- 鎓 -1- 基 ) 丙酸 2,2,2- 三氟乙酸鹽 A4 的製備 
在氮氣氣氛下，向2-嗒𠯤-4-基喹㗁啉（0.5 g）在乙腈（24 mL）中的混合物中添加3-溴丙酸甲基酯（0.78 mL）。將混合物在80°C下加熱16小時，冷卻至室溫並且濃縮，以得到粗3-(4-喹㗁啉-2-基嗒𠯤-1-鎓-1-基)丙酸甲酯溴化物，將其不經進一步純化而使用。 步驟2：3-(4-喹㗁啉-2-基嗒𠯤-1-鎓-1-基)丙酸 2,2,2-三氟乙酸鹽A4的製備Under a nitrogen atmosphere, to a mixture of 2-taza-4-ylquinoline (0.5 g) in acetonitrile (24 mL) was added methyl 3-bromopropionate (0.78 mL). The mixture was heated at 80°C for 16 hours, cooled to room temperature and concentrated to obtain crude methyl 3-(4-quinolin-2-yl-onium-1-yl)propionate bromide , It was used without further purification. Step 2: Preparation of 3-(4-quinoline-2-yl-onium-1-yl)propionic acid 2,2,2-trifluoroacetate A4
將3-(4-喹㗁啉-2-基嗒𠯤-1-鎓-1-基)丙酸甲酯溴化物（0.9 g）和濃的含水鹽酸（17 mL）的混合物在80°C下加熱4小時。冷卻至室溫之後，將反應混合物濃縮並且藉由製備型逆相HPLC（洗提液中存在三氟乙酸）純化，以得到3-(4-喹㗁啉-2-基嗒𠯤-1-鎓-1-基)丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400MHz, CD3
OD) 10.48 (d, 1H), 10.08 (d, 1H), 9.83 (s, 1H), 9.45 (dd, 1H), 8.30 - 8.37 (m, 1H), 8.21 -8.28 (m, 1H), 7.97 - 8.09 (m, 2H), 5.18 (t, 2H), 3.26 - 3.33 (m, 2H) (CO2
H質子缺失)實施例 5 ： 3-[4-(5,6,7,8- 四氫喹唑啉 -2- 基 ) 嗒 𠯤 -1- 鎓 -1- 基 ] 丙酸 2,2,2- 三氟乙酸鹽 A10 的製備 
在室溫下，向2-側氧基環己烷甲酸乙酯（5 g）在乙醇（100 mL）中的溶液中添加甲醇鈉（3.02 g）和脲（3.89 g）。在80°C下加熱28小時之後，將反應混合物冷卻至室溫並且濃縮。向粗產物中添加水（100 mL）並且將混合物用乙酸乙酯（3 × 250 mL）萃取。將合併的有機相用鹽水洗滌、經硫酸鈉乾燥、濃縮並且藉由矽膠管柱層析純化，以得到呈白色固體的5,6,7,8-四氫-1H-喹唑啉-2,4-二酮。1
H NMR (400MHz, DMSO-d6
) 10.88 (br s, 1H), 10.60 (br s, 1H), 2.29 (t, 2H), 2.13 (t, 2H), 1.47-1.68 (m, 4H)
步驟2：2,4-二氯-5,6,7,8-四氫喹唑啉的製備
將5,6,7,8-四氫-1H-喹唑啉-2,4-二酮（3.5 g）和三氯氧磷（48 g）的混合物在室溫下攪拌30分鐘，然後在100°C下加熱3小時。冷卻至室溫之後，將反應混合物濃縮並且將殘餘物傾倒入飽和碳酸氫鈉溶液（200 mL）中。將所得固體過濾出並且藉由矽膠管柱層析（用在環己烷中50%乙酸乙酯洗提）純化，以得到呈米色固體的2,4-二氯-5,6,7,8-四氫喹唑啉。1
H NMR (400MHz, CDCl3
) 2.82-2.94 (m, 2H), 2.67-2.78 (m, 2H), 1.82-1.93 (m, 4H))
步驟3：2-氯-5,6,7,8-四氫喹唑啉的製備
在室溫下，向2,4-二氯-5,6,7,8-四氫喹唑啉（1.4 g）在丙酮（20 mL）中的溶液中添加鋅粉（4.5 g），然後添加氯化銨（0.44 g）在水（20 mL）中的溶液。將反應混合物在90°C下攪拌1.5小時、冷卻至室溫並且通過矽藻土過濾。將濾液濃縮並且將殘餘物在二氯甲烷與水之間分配。將有機相濃縮並且藉由矽膠管柱層析（用在環己烷中30%乙酸乙酯洗提）純化，以得到呈白色固體的2-氯-5,6,7,8-四氫喹唑啉。
1H NMR (400MHz, CDCl3
) 8.28 (s, 1H), 2.88 (t, 2H), 2.74 (t, 2H), 1.78-1.94 (m, 4H)
步驟4：2-嗒𠯤-4-基-5,6,7,8-四氫喹唑啉的製備
將2-氯-5,6,7,8-四氫喹唑啉（0.65 g）、4-(三丁基錫烷基)嗒𠯤（1.71g）和四(三苯基膦)鈀(0)（0.67g）在1,4-二㗁𠮿（13 mL）中的混合物在130°C下、在微波輻射、氮氣氣氛, 下加熱1小時。將反應混合物冷卻至室溫，通過矽藻土過濾並且濃縮。將粗產物藉由矽膠管柱層析（用在二氯甲烷中5%甲醇洗提）純化，以得到呈淺黃色固體的2-嗒𠯤-4-基-5,6,7,8-四氫喹唑啉。1 H NMR (CDCl3 ) 10.12 (s, 1H), 9.32 (d, 1H), 8.53 (s, 1H), 8.38 (dd, 1H), 2.97 (t, 2H), 2.83 (t, 2H), 1.86-2.00 (m, 4H) 步驟5：3-[4-(5,6,7,8-四氫喹唑啉-2-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽A10的製備Combine 2-chloro-5,6,7,8-tetrahydroquinazoline (0.65 g), 4-(tributylstannyl) titan (1.71g) and tetrakis(triphenylphosphine) palladium (0) ( 0.67g) The mixture in 1,4-Di㗁𠮿 (13 mL) was heated at 130°C under microwave radiation and nitrogen atmosphere for 1 hour. The reaction mixture was cooled to room temperature, filtered through Celite and concentrated. The crude product was purified by silica gel column chromatography (eluted with 5% methanol in dichloromethane) to obtain 2-taka-4-yl-5,6,7,8-tetra as a pale yellow solid Hydroquinazoline. 1 H NMR (CDCl 3 ) 10.12 (s, 1H), 9.32 (d, 1H), 8.53 (s, 1H), 8.38 (dd, 1H), 2.97 (t, 2H), 2.83 (t, 2H), 1.86 -2.00 (m, 4H) Step 5: 3-[4-(5,6,7,8-Tetrahydroquinazolin-2-yl)pyridine-1-ium-1-yl]propionic acid 2,2 , Preparation of 2-Trifluoroacetate A10
向2-嗒𠯤-4-基-5,6,7,8-四氫喹唑啉（0.25 g）在乙腈（2.5 mL）中的溶液中添加3-溴丙酸（0.37 g）並且將反應混合物在85°C下加熱16小時。將反應混合物冷卻至室溫並且濃縮。將殘餘物用三級丁基甲基醚洗滌並且藉由製備型逆相HPLC （洗提液中存在三氟乙酸）純化，以得到呈棕色膠狀物的3-[4-(5,6,7,8-四氫喹唑啉-2-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400MHz, D2
O) 10.19 (d, 1H), 9.89 (d, 1H), 9.18 (dd, 1H), 8.72 (s, 1H), 5.19 (t, 2H), 3.33 (t, 2H), 3.01 (t, 2H), 2.91 (t, 2H), 1.92-1.99 (m, 2H), 1.84-1.92 (m, 2H) (CO2
H質子缺失)實施例 6 ： 3-(4- 㗁唑并 [5,4-b] 吡啶 -2- 基嗒 𠯤 -1- 鎓 -1- 基 ) 丙酸 2,2,2- 三氟乙酸鹽 A14 的製備 
在0°C，在氮氣氣氛下，向嗒𠯤-4-甲酸（10 g）在二氯甲烷（100 mL）中的溶液中添加五氟苯酚（14.38 g），然後添加N
-(3-二甲基胺基丙基)-N
′-乙基碳二亞胺鹽酸鹽（17.98 g）和N,N
-二甲基胺基吡啶（1.92 g）。在室溫下攪拌18小時之後，將反應混合物用水稀釋，用乙酸乙酯（3 × 250 mL）萃取。將合併的有機相經硫酸鈉乾燥、濃縮並且藉由矽膠管柱層析純化，以得到呈白色固體的(五氟苯基)嗒𠯤-4-甲酸酯。1
H NMR (400 MHz, CDCl3
) 9.82 -9.89 (m, 1H), 9.61 (dd, 1H), 8.19 (dd, 1H)
步驟2：N
-(2-氯-3-吡啶基)嗒𠯤-4-甲醯胺的製備
向(2,3,4,5,6-五氟苯基)嗒𠯤-4-甲酸酯（2.5 g）在乙腈（25 mL）中溶液中添加2-氯吡啶-3-胺（1.7 g），然後在150°C下在微波輻射下加熱2小時。將反應混合物濃縮並且用乙酸乙酯（3 × 120 mL）萃取。將合併的有機相經硫酸鈉乾燥、濃縮並且將殘餘物用三級丁基甲基醚洗滌，以得到呈固體的N
-(2-氯-3-吡啶基)嗒𠯤-4-甲醯胺。1
H NMR (400MHz, CDCl3
) 9.67 (s, 1H), 9.51 (d, 1H), 8.85 (dd, 1H), 8.47 (br s, 1H), 8.24 (dd, 1H), 7.92 (dd, 1H), 7.38 (dd, 1H)
步驟3：2-嗒𠯤-4-基㗁唑并[5,4-b]吡啶的製備
向N -(2-氯-3-吡啶基)嗒𠯤-4-甲醯胺（1 g）在四氫呋喃（15 mL）中的溶液中添加碘化銅（0.024 g）、1,10-啡啉（0.054 g）和碳酸鉀（0.46 g）然後在140°C下在微波輻射下加熱2小時。將反應混合物冷卻至室溫並且用乙酸乙酯（3 × 90 mL）萃取。將合併的有機相用水洗滌，經硫酸鈉乾燥並且濃縮，以得到呈棕色固體的2-嗒𠯤-4-基㗁唑并[5,4-b]吡啶。1 H NMR (400MHz, CDCl3 ) 10.01 (s, 1H), 9.49 (d, 1H), 8.50 (dd, 1H), 8.30 - 8.15 (m, 2H), 7.48 (dd, 1H) 步驟4：3-(4-㗁唑并[5,4-b]吡啶-2-基嗒𠯤-1-鎓-1-基)丙酸 2,2,2-三氟乙酸鹽A14的製備Add copper iodide (0.024 g) and 1,10-phenanthroline to a solution of N -(2-chloro-3-pyridinyl) tetraformamide (1 g) in tetrahydrofuran (15 mL) (0.054 g) and potassium carbonate (0.46 g) were then heated at 140°C under microwave radiation for 2 hours. The reaction mixture was cooled to room temperature and extracted with ethyl acetate (3×90 mL). The combined organic phases were washed with water, dried over sodium sulfate, and concentrated to give 2-tazolo[5,4-b]pyridine as a brown solid. 1 H NMR (400MHz, CDCl 3 ) 10.01 (s, 1H), 9.49 (d, 1H), 8.50 (dd, 1H), 8.30-8.15 (m, 2H), 7.48 (dd, 1H) Step 4: 3- Preparation of (4-azolo[5,4-b]pyridin-2-yl-onium-1-yl)propionic acid 2,2,2-trifluoroacetate A14
向2-嗒𠯤-4-基㗁唑并[5,4-b]吡啶（0.5 g）在乙腈（5 mL）中的溶液中添加3-溴丙酸（0.59 g）並且將反應混合物在85°C下加熱16小時。冷卻至室溫之後，將反應混合物濃縮並且將殘餘物用三級丁基甲基醚洗滌。將粗產物藉由製備型逆相HPLC （洗提液中存在三氟乙酸）純化，以得到呈膠狀物的3-(4-㗁唑并[5,4-b]吡啶-2-基嗒𠯤-1-鎓-1-基)丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400MHz, D2
O) 10.22 (d, 1H), 10.04 (d, 1H), 9.27-9.25 (m, 1H), 8.59 (dd, 1H), 8.46 (dd, 1H), 7.70 (dd, 1H), 5.22 (t, 2H), 3.22 (t, 2H) (CO2
H質子缺失)實施例 7 ： 3-[4-(1,2,4- 苯并三 𠯤 -3- 基 ) 嗒 𠯤 -1- 鎓 -1- 基 ] 丙酸 2,2,2- 三氟乙酸鹽 A15 的製備 
在室溫下向嗒𠯤-4-甲酸甲酯（2 g）在乙醇（50 mL）中的溶液中添加水合肼（0.8 mL）。將反應混合物在室溫下攪拌16小時，然後濃縮。將殘餘物用三級丁基甲基醚洗滌，以得到呈棕色固體的嗒𠯤-4-甲醯肼。1
H NMR (400 MHz, DMSO-d6
) 10.30 (br s, 1H), 9.51 (dd, 1H), 9.41 (dd, 1H), 7.96 (dd, 1H), 4.73 (br s, 2H)
步驟2：3-嗒𠯤-4-基-1,2,4-苯并三𠯤的製備
在室溫下，向2-碘苯胺（1 g）在1,4-二㗁𠮿（10 mL）和N,N -二甲基甲醯胺（10 mL）的混合物中的溶液中添加嗒𠯤-4-甲醯肼（0.94 g）。向此混合物中添加碳酸銫（3 g）和氧化銅(I)（0.069 g），然後在90°C加熱6小時。在冷卻至室溫之後，將該反應混合物用水進行淬滅，並且用乙酸乙酯（3 × 100 mL）萃取。將合併的有機相經硫酸鈉乾燥、濃縮並且藉由矽膠管柱層析純化，以得到呈棕色固體的3-嗒𠯤-4-基-1,2,4-苯并三𠯤。1 H NMR (400 MHz, CDCl3 ) 10.45 (dd, 1H), 9.51 (dd, 1H), 8.78 (dd, 1H), 8.66 (dd, 1H), 8.23 (dd, 1H), 8.09 - 8.18 (m, 1H), 7.99 - 8.06 (m, 1H) 步驟3：3-[4-(1,2,4-苯并三𠯤-3-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽A15的製備At room temperature, to a solution of 2-iodoaniline (1 g) in a mixture of 1,4-dimethan (10 mL) and N,N -dimethylformamide (10 mL), add a -4-methylhydrazine (0.94 g). To this mixture were added cesium carbonate (3 g) and copper (I) oxide (0.069 g), and then heated at 90°C for 6 hours. After cooling to room temperature, the reaction mixture was quenched with water and extracted with ethyl acetate (3×100 mL). The combined organic phases were dried over sodium sulfate, concentrated, and purified by silica gel column chromatography to obtain 3-taza-4-yl-1,2,4-benzotriazathine as a brown solid. 1 H NMR (400 MHz, CDCl 3 ) 10.45 (dd, 1H), 9.51 (dd, 1H), 8.78 (dd, 1H), 8.66 (dd, 1H), 8.23 (dd, 1H), 8.09-8.18 (m , 1H), 7.99-8.06 (m, 1H) Step 3: 3-[4-(1,2,4-Benzotris-3-yl)pada-1-ium-1-yl]propionic acid 2 Preparation of 2,2-trifluoroacetate A15
向3-嗒𠯤-4-基-1,2,4-苯并三𠯤（0.2 g）在乙腈（4.0 mL）中的溶液中添加 3-溴丙酸（0.31 g）然後在80°C下加熱40小時。冷卻至室溫之後，將反應混合物濃縮、用三級丁基甲基醚洗滌並且藉由製備型逆相HPLC （洗提液中存在三氟乙酸）純化，以得到呈棕色固體的3-[4-(1,2,4-苯并三𠯤-3-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400MHz, D2
O) 10.53 (d, 1H), 10.02 (d, 1H), 9.58 (dd, 1H), 8.61 (d, 1H), 8.24 (d, 2H), 8.14 (dd, 1H), 5.22 (t, 2H), 3.33 (t, 2H) (CO2
H質子缺失)實施例 8 ： 3-[4-([1,2,4] 三唑并 [4,3-b] 嗒 𠯤 -3- 基 ) 嗒 𠯤 -1- 鎓 -1- 基 ] 丙酸 2,2,2- 三氟乙酸鹽 A16 的製備 
向嗒𠯤-4-甲醯肼（1.1 g）在1,4-二㗁𠮿（22 mL）中的溶液中添加3-溴嗒𠯤（1.3 g）並且將反應混合物在150°C下在微波輻射下加熱1.5小時。冷卻至室溫之後，將反應混合物濃縮並且藉由矽膠管柱層析（用在二氯甲烷中15%甲醇洗提）純化，以得到呈固體的3-嗒𠯤-4-基-[1,2,4]三唑并[4,3-b]嗒𠯤。To a solution of tetramethylhydrazine (1.1 g) in 1,4-dimethan (22 mL), add 3-bromo hydrazine (1.3 g) and place the reaction mixture at 150°C in the microwave Heat for 1.5 hours under radiation. After cooling to room temperature, the reaction mixture was concentrated and purified by silica gel column chromatography (eluted with 15% methanol in dichloromethane) to obtain 3-ph-4-yl-[1, 2,4]triazolo[4,3-b]ta 𠯤.
1 H NMR (400MHz, DMSO-d6 ) 10.14 (dd, 1H), 9.52 (dd, 1H), 8.90 (dd, 1H), 8.54-8.69 (m, 2H), 7.57 (dd, 1H)。 步驟2：3-[4-([1,2,4]三唑并[4,3-b]嗒𠯤-3-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽A16的製備 1 H NMR (400MHz, DMSO-d 6 ) 10.14 (dd, 1H), 9.52 (dd, 1H), 8.90 (dd, 1H), 8.54-8.69 (m, 2H), 7.57 (dd, 1H). Step 2: 3-[4-([1,2,4]triazolo[4,3-b]daza-3-yl)daz-1-ium-1-yl]propionic acid 2,2, Preparation of 2-trifluoroacetate A16
向3-嗒𠯤-4-基-[1,2,4]三唑并[4,3-b]嗒𠯤（0.25 g）在乙腈（5 mL）中的溶液中添加3-溴丙酸（0.38 g），然後在85°C下加熱48小時。將反應混合物濃縮、用三級丁基甲基醚（50 mL）洗滌並且藉由製備型逆相HPLC（洗提液中存在三氟乙酸）純化，以得到呈棕色膠狀物的3-[4-([1,2,4]三唑并[4,3-b]嗒𠯤-3-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400 MHz, D2
O) 10.44 (d, 1H), 9.94 (d, 1H), 9.60 (dd, 1H), 8.92 (d, 1H), 8.49 (d, 1H), 7.69 (dd, 1H), 5.19 (t, 2H), 3.34 (t, 2H) (CO2
H質子缺失)實施例 9 ： 3-[4-(3- 甲基 -[1,2,4] 三唑并 [4,3-a] 吡 𠯤 -8- 基 ) 嗒 𠯤 -1- 鎓 -1- 基 ] 丙酸 2,2,2- 三氟乙酸鹽的製備 
向2,3-二氯吡𠯤（2 g）在乙醇（6 mL）中的溶液 中添加水合肼（0.6 mL）然後在室溫下攪拌16小時。將反應混合物濃縮並且用三級丁基甲基醚洗滌，以得到呈棕色固體的(3-氯吡𠯤-2-基)肼。1
H NMR (400MHz, DMSO-d6
) 8.06 (d, 1H), 7.56 (d, 1H) (三個NH質子缺失)
步驟2：N
,3-二甲基嗒𠯤-4-甲醯胺的製備
將(3-氯吡𠯤-2-基)肼（1 g）在原乙酸三甲酯（13 mL）中的溶液在130°C下加熱3小時。冷卻至室溫之後，將反應混合物濃縮並且將殘餘物用三級丁基甲基醚洗滌，以得到呈紅色固體的8-氯-3-甲基-[1,2,4]三唑并[4,3-a]吡𠯤。1
H NMR (400MHz, DMSO-d6
) 8.53 (d, 1H), 7.77 (d, 1H), 2.75 (s, 3H)
步驟3：3-甲基-8-嗒𠯤-4-基-[1,2,4]三唑并[4,3-a]吡𠯤的製備
在室溫下,在氮氣氣氛下，向8-氯-3-甲基-[1,2,4]三唑并[4,3-a]吡𠯤（0.5 g）在甲苯（10 mL）中的溶液中添加三丁基(嗒𠯤-4-基)錫烷（1.2 g）和四(三苯基膦)鈀(0)（0.34 g）。將反應混合物在90°C下加熱18小時，冷卻至室溫並且濃縮。將粗產物藉由矽膠管柱層析純化，以得到呈灰白色固體的3-甲基-8-嗒𠯤-4-基-[1,2,4]三唑并[4,3-a]吡𠯤。1 H NMR (400 MHz, CD3 OD) 10.38 (dd, 1H), 9.47 (dd, 1H), 9.12 (dd, 1H), 8.47 (d, 1H), 8.19 (d, 1H), 2.87 (s, 3H) 步驟4：3-[4-(3-甲基-[1,2,4]三唑并[4,3-a]吡𠯤-8-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽A17的製備At room temperature, in a nitrogen atmosphere, add 8-chloro-3-methyl-[1,2,4]triazolo[4,3-a]pyridine (0.5 g) in toluene (10 mL) Add tributyl(tada-4-yl)stannane (1.2 g) and tetrakis(triphenylphosphine)palladium(0)(0.34 g) to the solution. The reaction mixture was heated at 90°C for 18 hours, cooled to room temperature and concentrated. The crude product was purified by silica gel column chromatography to obtain 3-methyl-8-tado-4-yl-[1,2,4]triazolo[4,3-a]pyridine as an off-white solid 𠯤. 1 H NMR (400 MHz, CD 3 OD) 10.38 (dd, 1H), 9.47 (dd, 1H), 9.12 (dd, 1H), 8.47 (d, 1H), 8.19 (d, 1H), 2.87 (s, 3H) Step 4: 3-[4-(3-Methyl-[1,2,4]triazolo[4,3-a]pyrazol-8-yl)praz-1-on-1-yl ] Preparation of 2,2,2-trifluoroacetate A17 of propionic acid
在室溫下，向3-甲基-8-嗒𠯤-4-基-[1,2,4]三唑并[4,3-a]吡𠯤（0.25 g）在乙腈（5 mL）中的溶液中添加3-溴丙酸（0.38 g）。將反應混合物在80°C下加熱40小時，冷卻至室溫，然後濃縮。將殘餘物藉由製備型逆相HPLC （洗提液中存在三氟乙酸）純化，以得到呈灰白色固體的3-[4-(3-甲基-[1,2,4]三唑并[4,3-a]吡𠯤-8-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400MHz, D2
O) 10.43 (d, 1H), 9.98 (d, 1H), 9.67 (dd, 1H), 8.5 (d, 1H), 8.28 (d, 1H), 5.19 (t, 2H), 3.31 (t, 2H), 2.83 (s, 3H) (CO2
H質子缺失)實施例 10 ： 3-[4-([1,2,4] 三唑并 [4,3-a] 吡啶 -3- 基 ) 嗒 𠯤 -1- 鎓 -1- 基 ] 丙酸 2,2,2- 三氟乙酸鹽 A18 的製備 
向(五氟苯基)嗒𠯤-4-甲酸酯（0.4 g）在乙腈（4 mL）中的溶液中添加2-吡啶基肼（0.22 g）並且將反應混合物在室溫下攪拌15分鐘。將所得沈澱物過濾出並且用三級丁基醚洗滌，以得到呈固體的N’
-(2-吡啶基)嗒𠯤-4-甲醯肼。1
H NMR (400 MHz, DMSO-d6
) 10.59 - 11.11 (m, 1H), 9.62 (dd, 1H), 9.49 (dd, 1H), 8.69 (br s, 1H), 8.06-8.10 (m, 2H), 7.56 (t, 1H), 6.71- 6.77 (m, 2H)
步驟2：3-嗒𠯤-4-基-[1, 2, 4] 三唑并 [4, 3-a] 吡啶的製備
將N' -(2-吡啶基)嗒𠯤-4-甲醯肼（0.3 g）在乙酸（3 mL）中的溶液在180°C下在微波輻射下加熱30分鐘。冷卻至室溫之後，將反應混合物濃縮並且將殘餘物用三級丁基甲基醚洗滌，以得到呈固體的3-嗒𠯤-4-基-[1,2,4]三唑并[4,3-a]吡啶。1 H NMR (400 MHz, CDCl3 ) 9.83 (s, 1H), 9.47 (d, 1H), 8.43 (d, 1H), 8.05 (dd, 1H), 7.96-8.01 (m, 1H), 7.46 (t 1H), 7.10 (t, 1H) 步驟3：3-[4-([1,2,4]三唑并[4,3-a]吡啶-3-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽A18的製備A solution of N' -(2-pyridyl)papain (0.3 g) in acetic acid (3 mL) was heated at 180°C under microwave irradiation for 30 minutes. After cooling to room temperature, the reaction mixture was concentrated and the residue was washed with tertiary butyl methyl ether to obtain 3-[1,2,4]triazolo[4,3] as a solid -a] Pyridine. 1 H NMR (400 MHz, CDCl 3 ) 9.83 (s, 1H), 9.47 (d, 1H), 8.43 (d, 1H), 8.05 (dd, 1H), 7.96-8.01 (m, 1H), 7.46 (t 1H), 7.10 (t, 1H) Step 3: 3-[4-([1,2,4]triazolo[4,3-a]pyridin-3-yl)pada-1-ium-1- Preparation of 2,2,2-trifluoroacetate A18 of propionic acid
向3-嗒𠯤-4-基-[1, 2, 4]三唑并[4,3-a]吡啶（0.2 g）在乙腈（3 mL）中的溶液中添加3-溴丙酸（0.16 g）並且將反應混合物在60°C下加熱24小時。冷卻至室溫之後，將反應混合物濃縮並且將殘餘物 藉由製備型逆相HPLC（洗提液中存在三氟乙酸）純化，以得到呈固體的3-[4-([1,2,4]三唑并[4,3-a]吡啶-3-基)嗒𠯤-1-鎓-1-基]丙酸 2,2,2-三氟乙酸鹽。1
H NMR (400MHz, D2
O) 10.04 (d, 1H), 9.83 (d, 1H), 9.00 (dd, 1H), 8.81 (d, 1H), 7.95 (d, 1H), 7.71 (dd, 1H), 7.33 (t, 1H), 5.09 (t, 2H), 3.25 (t, 2H) (CO2
H質子缺失)實施例 11 ： 1- 甲基 -6- 嗒 𠯤 -4- 基 - 吡唑并 [3,4-d] 嘧啶的製備 
在氮氣氣氛下，將6-氯-1-甲基-吡唑并[3,4-d]嘧啶（0.81 g）在N,N -二甲基甲醯胺（15 mL）中的溶液冷卻至約0°C並且分批添加氫化鈉（在礦物油中60%，0.58 g）。在約0°C下攪拌15分鐘之後，然後添加碘甲烷（1.2 mL）。允許將該反應混合物加溫至室溫並再攪拌4小時。Under a nitrogen atmosphere, a solution of 6-chloro-1-methyl-pyrazolo[3,4-d]pyrimidine (0.81 g) in N,N -dimethylformamide (15 mL) was cooled to About 0°C and add sodium hydride (60% in mineral oil, 0.58 g) in portions. After stirring for 15 minutes at about 0°C, methyl iodide (1.2 mL) was then added. The reaction mixture was allowed to warm to room temperature and stirred for another 4 hours.
將混合物用水進行淬滅，並且用乙酸乙酯進行萃取。將有機相經硫酸鈉乾燥、濃縮並且藉由矽膠管柱層析（用乙酸乙酯在己烷中的混合物洗提）純化，以得到呈白色固體的6-氯-1-甲基-吡唑并[3,4-d]嘧啶。1 H NMR (400 MHz, CDCl3 ) 9.05 (s, 1H), 8.16 (s, 1H), 4.14 (s, 3H) 步驟2：1-甲基-6-嗒𠯤-4-基-吡唑并[3,4-d]嘧啶的製備The mixture was quenched with water, and extracted with ethyl acetate. The organic phase was dried over sodium sulfate, concentrated and purified by silica gel column chromatography (eluted with a mixture of ethyl acetate in hexane) to obtain 6-chloro-1-methyl-pyrazole as a white solid And [3,4-d]pyrimidine. 1 H NMR (400 MHz, CDCl 3 ) 9.05 (s, 1H), 8.16 (s, 1H), 4.14 (s, 3H) Step 2: 1-Methyl-6-tado-4-yl-pyrazolo Preparation of [3,4-d]pyrimidine
將三丁基(嗒𠯤-4-基)錫烷（1.839 g）、6-氯-1-甲基-吡唑并[3,4-d]嘧啶（0.7 g）和四(三苯基膦)鈀(0)（0.481 g）在1,4-二㗁𠮿（7 mL）中的混合物在氮氣氣氛下在150°C下在微波輻射下加熱1小時。將反應混合物冷卻至室溫、濃縮並且藉由矽膠管柱層析（用甲醇在二氯甲烷中的混合物）純化，以得到呈固體的1-甲基-6-嗒𠯤-4-基-吡唑并[3,4-d]嘧啶。1
H NMR (400 MHz, CDCl3
) 10.29 (s, 1H), 9.40 (d, 1H), 9.31 (s, 1H), 8.57-8.59 (m, 1H), 8.22 (s, 1H), 4.23 (s, 3H)實施例 12 ： 1- 甲基 -6- 嗒 𠯤 -4- 基 - 三唑并 [4,5-c] 嗒 𠯤 的製備 
在氮氣氣氛下，在室溫下，向3,4,6-三氯嗒𠯤（0.5 g）在四氫呋喃（5 mL）中的溶液中添加甲基胺（2.7 mL，2M在四氫呋喃中）。將反應混合物在室溫下攪拌2小時，然後濃縮。將殘餘物藉由矽膠管柱層析（用在環己烷中30%乙酸乙酯洗提）純化，以得到呈白色固體的3,6-二氯-N
-甲基-嗒𠯤-4-胺。1
H NMR (400MHz, DMSO-d6
) 7.35 (br s, 1H), 6.88 (s, 1H), 2.80 (d, 3H)
步驟2：3-氯-5-(甲基胺基)-1H-嗒𠯤-6-酮腙的製備
將3,6-二氯-N
-甲基-嗒𠯤-4-胺（3.5 g）和水合肼（18 mL）的混合物在60°C下加熱2小時。將反應混合物用水（100 mL）稀釋並且將所得沈澱物過濾並且用三級丁基甲基醚（3 × 100 mL）洗滌，以得到呈白色固體的3-氯-5-(甲基胺基)-1H-嗒𠯤-6-酮腙。
LCMS：174 (M+H)+
步驟3：6-氯-N
4-甲基-嗒𠯤-3,4-二胺的製備
在氮氣氣氛下，向3-氯-5-(甲基胺基)-1H-嗒𠯤-6-酮腙（2 g）在乙醇（300 mL）中的溶液中添加雷尼鎳（3.38 g）。將反應混合物然後在氫氣氣氛（1巴）下在室溫下攪拌7小時。將反應混合物過濾並且將濾液濃縮，以得到呈淺黃色固體的6-氯-N
4-甲基-嗒𠯤-3,4-二胺。1
H NMR (400MHz, DMSO-d6
) 6.48 (br s, 1H), 6.28 (s, 1H), 6.07 (br s, 2H), 2.76 (d, 3H)
步驟4：6-氯-1-甲基-三唑并[4,5-c]嗒𠯤的製備
在0°C下，向6-氯-N 4-甲基-嗒𠯤-3,4-二胺（1 g）在6 M含水鹽酸（8 mL）中的溶液中添加硝酸鈉（0.47 g）在水（2 mL）中的溶液。將反應混合物在室溫下攪拌2小時然後用水性氫氧化銨鹼化並且用乙酸乙酯（3 × 120 mL）萃取。將合併的有機相經硫酸鈉乾燥、濃縮並且藉由矽膠管柱層析（用在環己烷中40%乙酸乙酯洗提）純化，以得到呈淺粉色固體的6-氯-1-甲基-三唑并[4,5-c]嗒𠯤。1 H NMR (400MHz, DMSO-d6 ) 8.68 (s, 1H), 4.35 (s, 3H) 步驟5：1-甲基-6-嗒𠯤-4-基-三唑并[4,5-c]嗒𠯤的製備At 0°C, add sodium nitrate (0.47 g) to a solution of 6-chloro- N 4-methyl-tado-3,4-diamine (1 g) in 6 M aqueous hydrochloric acid (8 mL) Solution in water (2 mL). The reaction mixture was stirred at room temperature for 2 hours and then basified with aqueous ammonium hydroxide and extracted with ethyl acetate (3×120 mL). The combined organic phase was dried over sodium sulfate, concentrated and purified by silica gel column chromatography (eluted with 40% ethyl acetate in cyclohexane) to obtain 6-chloro-1-methyl as a pale pink solid Base-triazolo [4,5-c] 𠯤. 1 H NMR (400MHz, DMSO-d 6 ) 8.68 (s, 1H), 4.35 (s, 3H) Step 5: 1-Methyl-6-tado-4-yl-triazolo[4,5-c ]Da𠯤 preparation
將三丁基(嗒𠯤-4-基)錫烷（0.48 g）、6-氯-1-甲基-三唑并[4,5-c]嗒𠯤（0.2 g）和四(三苯基膦)鈀(0)（0.137 g）在1,4-二㗁𠮿（4 mL）中的混合物在氮氣氣氛下、在130°C下在微波輻射下加熱30分鐘。將反應混合物冷卻至室溫、濃縮並且用三級丁基甲基醚洗滌，以得到1-甲基-6-嗒𠯤-4-基-三唑并[4,5-c]嗒𠯤。1 H NMR (400MHz, DMSO-d6 ) 10.08-10.09 (dd, 1H), 10.03 - 10.12 (m, 1H), 9.50 (d, 1H), 8.52 (dd, 1H), 4.44 (s, 3H)Combine tributyl(taka-4-yl)stannane (0.48 g), 6-chloro-1-methyl-triazolo[4,5-c]taka (0.2 g) and tetrakis(triphenyl) A mixture of phosphine) palladium(0) (0.137 g) in 1,4-dipyridine (4 mL) was heated at 130°C under microwave irradiation for 30 minutes under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, concentrated, and washed with tertiary butyl methyl ether to obtain 1-methyl-6-taza-4-yl-triazolo[4,5-c]taza. 1 H NMR (400MHz, DMSO-d 6 ) 10.08-10.09 (dd, 1H), 10.03-10.12 (m, 1H), 9.50 (d, 1H), 8.52 (dd, 1H), 4.44 (s, 3H)
表A中的其他化合物係藉由類似程序從適當的起始材料製備。
[表 A
]- 本發明的化合物的物理數據 
將多種測試物種的種子播種在盆中的標準土壤中。在受控條件下、在溫室（在24°C/16°C下，白天/夜晚；14個小時光照；65%濕度）下培養14天後（出苗後），用如下得到的水性噴霧溶液噴灑植物：將具有式 (I) 之技術活性成分在少量丙酮和稱為IF50（11.12% Emulsogen EL360 TM+44.44% N-甲基吡咯啶酮+44.44% Dowanol DPM乙二醇醚）的特殊溶劑和乳化劑混合物中溶解，以製備50 g/l溶液，然後使用0.25%或1% Empicol ESC70（月桂基醚硫酸鈉）+ 1%硫酸銨在水中的溶液作為稀釋劑將其稀釋至所需濃度。Seeds of various test species were sown in standard soil in pots. After culturing for 14 days (post-emergence) in a greenhouse (at 24°C/16°C, day/night; 14 hours of light; 65% humidity) under controlled conditions, spray with the aqueous spray solution obtained as follows Plants: The technical active ingredient of formula (I) is emulsified in a small amount of acetone and a special solvent called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) To prepare a 50 g/l solution, and then use 0.25% or 1% Empicol ESC70 (sodium laureth sulfate) + 1% ammonium sulfate in water as a diluent to dilute it to the desired concentration.
然後使該等測試植物在受控條件下、在溫室（在24°C/16°C下，白天/夜晚；14個小時光照；65%濕度）中生長，並且每日澆水兩次。13天後，評估試驗（100 = 全部的植物損害；0 = 無植物損害）。結果示於下表B中。測試植物：
牽牛花（IPOHE）、白苞猩猩草（EPHHL）、藜草（CHEAL）、長芒莧（AMAPA）、多年生黑麥草（LOLPE）、馬唐（DIGSA）、牛筋草（ELEIN）、稗草（ECHCG）、大狗尾草（SETFA）
[表 B
]藉由出苗後施用具有式 (I) 之化合物對雜草物種的控制
無no
無no
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