CN114885952A - 新型除草化合物 - Google Patents
新型除草化合物 Download PDFInfo
- Publication number
- CN114885952A CN114885952A CN202210564046.0A CN202210564046A CN114885952A CN 114885952 A CN114885952 A CN 114885952A CN 202210564046 A CN202210564046 A CN 202210564046A CN 114885952 A CN114885952 A CN 114885952A
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- Prior art keywords
- methyl
- ethyl
- pyrazosulfuron
- populus
- imazachlor
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- BACHBFVBHLGWSL-UHFFFAOYSA-N methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-UHFFFAOYSA-N 0.000 claims description 3
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- A—HUMAN NECESSITIES
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Abstract
本申请涉及新型除草化合物。本公开涉及FR901464和/或思普力西欧他汀(spliceostatin)C化合物及其作为除草剂的用途。此外,本发明涉及用于作物保护的组合物和用于控制不想要的植被的方法。
Description
本申请是申请日为2018年9月6日、申请号为201880057959.5、发明名称为“新型除草化合物”的发明专利申请的分案申请。
技术领域
本公开整体上涉及一种使用已知用作抗菌剂和抗肿瘤剂的FR901464和/或思普力西欧他汀(spliceostatin)C的新方法。更具体地,其涉及用于控制和抑制单子叶、苔草或双子叶杂草的出苗和/或生长的方法、组合物和代谢物。
背景技术
天然产物是由微生物、植物和其他生物体产生的物质。微生物天然产物提供化学多样性的丰富来源,并且将天然产物用于药物目的历史由来已久。一些此类化合物是FR901464和思普力西欧他汀C,已发现其可用作抗菌剂和抗肿瘤剂。这些化合物是通过结合到U2 snRNA亚复合体的SF3b亚基(剪接体的重要组分)来抑制真核生物RNA剪接的超强抑制剂。
发明内容
本文提供了一种用于通过施用有效量的以下物质来控制杂草的方法:a)具有通式(I)的化合物
其中X、Y和Z各自独立地是-O、-NR或-S,其中R是H或C1-C10烷基;R1、R2、R3、R4、R5、R6、R7、R8、R11、R12和R13各自独立地是H、烷基、取代的烷基、烷基羧酸、烯基、取代的烯基、炔基、取代的炔基、芳基、取代的芳基、杂芳基、取代的杂芳基、杂环、取代的杂环、环烷基、取代的环烷基、烷氧基、取代的烷氧基、硫代烷基、取代的硫代烷基、羟基、卤素、氨基、酰胺基、羧基、-C(O)H、酰基、氧酰基、氨基甲酸酯、磺酰基、磺酰胺或硫酰基;和b)载剂、稀释剂、表面活性剂、佐剂和/或其他除草化合物或抑制所述杂草的生长的其他杀虫剂中的至少一种。
在一个具体方面,根据以上方法,其中所述化合物可以具有结构:
在另一方面,所述方法可以包括选自由以下组成的群组的第一物质:以上列出的化合物中的一种或多种;和b)任选地第二物质,其中所述第二物质是化学或生物除草剂和/或杀虫剂,以及c)任选地载剂、稀释剂、表面活性剂或佐剂中的至少一种。
在又一方面,杂草通过抑制单子叶、苔草或双子叶杂草的出苗和/或生长来控制,包含向所述杂草或土壤施用有效抑制单子叶、苔草或双子叶杂草的出苗或生长的量的以下物质:(a)以上列出的化合物中的一种或多种,(b)任选地另一种物质,其中所述物质是化学或生物除草剂,或(c)以上列出的任何组合。
在一方面,所述其他除草化合物包括但不限于:丁香、肉桂、柠檬草、柑橘油、橙皮油、腾毒素、康奈西斯汀(cornexistin)、AAL-毒素、纤精酮、萨托明(thaxtomin)、假蒟亭碱、稻壳酮B、高粱酮(sorgoleone)、阿斯科拉毒素(ascaulatoxin)和阿斯科拉毒素阿格来康(ascaulatoxin aglycone)。化学除草剂可以包括但不限于氟吡草腙和其盐、麦草畏和其盐、苯唑草酮、环磺酮、S-异丙甲草胺、阿特拉津、甲基磺草酮、氟嘧磺隆、2,4-二氯苯氧基乙酸、烟嘧磺隆、噻吩磺隆、磺草灵、赛克津、禾草灵、吡氟禾草灵、精噁唑禾草灵、乙氧氟草醚、砜嘧磺隆、2甲4氯丙酸(mecoprop)和二氯喹啉酸、禾草丹、广灭灵、氰氟草酯、敌稗、苄嘧磺隆、五氟磺草胺、绿草定、咪草烟、氯吡嘧磺隆、二甲戊乐灵、双草醚、唑酮草酯、灭草松钠/三氟羧草醚钠、草甘膦、草丁膦、硬脂醇和/或嘧苯胺磺隆。
在又一方面,本发明公开的除草化合物与上述其他除草化合物表现出协同作用,如通过Colby公式所确定的,其中所述公式具有大于1的比率。
在一方面,所述杂草包括但不限于:籽粒苋(Amaranthus hypochondriacus)、反枝苋(Amaranthus retroflexus)、长芒苋(Amaranthus palmeri)、西部苋(Amaranthusrudis)、藜(Chenopodium album)、地肤(Kochia scoparia)、苘麻(Abutilontheophrasti)、欧锦葵(Malva sylvestris)、繁缕(Stellaria media)、马齿苋(Portulacaoleracea)、田旋花(Convolvulus arvensis)、圆叶牵牛(Ipomoea purpurea)、新疆白芥(Sinapis arvensis)、野萝卜(Raphanus raphanistrum)、天蓝苜蓿(Medicago lupulina)、白三叶草(Trifolium repens)、Genista monspessulana、柳兰(Epilobiumangustifolium)、龙葵(Solanum nigrum)、大狗尾草(Setaria faberi)、旱雀麦(Bromustectorum)、早熟禾(Poa annua)、草地早熟禾(Poa pratensis)、多花黑麦草(Loliummultiflorum)、马唐(Digitaria sanguinalis)、高羊茅(Festuca arundinaceae)、稗草(Echinochloa crus-galli)、长叶车前(Plantago lanceolata)、向日葵(Helianthusannuus)、豚草(Ambrosia artemisifolia)、雏菊(Bellis perennis)、药用蒲公英(Taraxacum officinale)、毒莴苣(Lactuca serriola)和/或莴苣(Lactuca sativa)。
在一个相关方面,本文提供了一种涂覆有上述一种或多种组合物的种子。所述种子可以是抗除草剂的遗传修饰的种子。
附图说明
为了更完全地理解本发明的特征和优点,现在参考本发明的详细描述以及附图,并且在附图中:
图1显示了长芒苋(Palmer amaranth)药害测试,其中Y轴为在4真叶期时处理并且在处理之后6天(DAT)评估的对长芒苋的损伤百分比,p<0.000并且Rsq=0.7887。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图2显示了长芒苋药害测试,其中Y轴为在6DAT时对4叶长芒苋植物进行的鲜重(g)/植物评估,p<0.000并且Rsq=0.7068。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图3显示了另一个长芒苋药害测试,在6DAT时对4叶长芒苋植物进行损伤百分比评估,p<0.000并且Rsq=0.7847。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图4显示了长芒苋药害测试,其中浓度与图3中相同。在6DAT时对4叶长芒苋植物进行鲜重(g)/植物评估,p<0.000并且Rsq=0.6305。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图5显示了又一个长芒苋药害测试。在6DAT时对4叶长芒苋植物进行损伤百分比评估,p<0.000并且Rsq=0.7239。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图6显示了与图5相同的实验,但是其中鲜重为Y轴。在6DAT时对4叶长芒苋植物进行鲜重(g)/植物评估,p<0.000并且Rsq=0.6330。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图7显示了又一个长芒苋药害测试。在6DAT时对4叶长芒苋植物进行损伤百分比评估,p<0.000并且Rsq=0.6521。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图8显示了与图7相同的实验,但是其中鲜重为Y轴。图2:在6DAT时对4叶长芒苋植物进行鲜重(g)/植物评估,p<0.000并且Rsq=0.6099。误差条表示标准误差。分组信息使用Fisher LSD法和90%置信。UTC=未处理对照。
图9显示了又一个长芒苋药害测试。在6DAT时对4叶长芒苋植物进行损伤百分比评估,p<0.000并且Rsq=0.9061。误差条表示标准误差。分组信息使用Fisher LSD法和95%置信。UTC=未处理对照。
图10显示了与图9相同的实验,但是其中鲜重为Y轴。在6DAT时对4叶长芒苋植物进行鲜重(g)/植物评估,p<0.000并且Rsq=0.8359。误差条表示标准误差。分组信息使用Fisher LSD法和95%置信。UTC=未处理对照。
图11显示了硬脂醇(HAVEN)与思普力西欧他汀C(MBI-014)之间的协同作用。UTC=未处理对照。
具体实施方式
虽然在此之前的组合物和方法易于具有各种修改和替代性形式,本文将详细描述示例性实施例。然而,应理解,不旨在将本发明限于所公开的具体形式,相反,旨在涵盖落在如所附权利要求限定的本发明的精神和范围内的所有修改、等效物和替代方案。
应理解,在提供值的范围的情况下,除非上下文另外明确指出,否则其中包括每个***值,到下限单位的十分之一。
除非另外定义,否则本文所用的所有技术和科学术语均具有与本发明所属领域中的普通技术人员通常所理解相同的含义。虽然在实践或测试本发明中也可使用与本文所述的方法和材料相似或等效的任何方法和材料,但是现在描述优选的方法和材料。
如本文所用,术语“包含(comprises)”、“包含(comprising)”、“包括(includes)”、“包括(including)”、“具有(has)”、“具有(having)”、“含有(contains)”、“含有(containing)”“特征在于”或其任何其他变型均旨在涵盖非排他性的包含,受限于明确指出的任何限制。例如,包含要素列表的组合物、混合物、工艺或方法不一定仅限于那些要素,而是可以包括未明确列出的或此类组合物、混合物、工艺或方法所固有的其他要素。
过渡短语“由……组成”不包括未指定的任何要素、步骤或成分。如果在权利要求书中,则这种短语将使权利要求不包括除所列举的那些以外的材料,与其通常相关联的杂质除外。当短语“由……组成”出现在权利要求主体的条款中,而不是紧跟在前言之后时,所述短语仅限制此条款中列出的要素;其他要素不从整个权利要求排除。
过渡短语“基本上由……组成”用于限定组合物、包括除确实公开的那些以外的材料、步骤、特征、组分或元素的方法,前提是这些额外的材料、步骤、特征、组分或元素实质上不影响所列主题的一种或多种基本和新型特征。术语“基本上由……组成”介于“包括”与“由……组成”之间。
如本文所用,术语“除草剂”意指控制或改变植物的生长的化合物。术语“除草有效量”意指这种化合物或此类化合物的组合的能够对植物生长产生控制或改变作用的量。控制或改变作用包括从自然发育的所有偏离作用,例如:杀伤、延迟、叶烧伤、白化病、矮化等。
术语“植物”是指植物的所有物理部分,包括种子、幼苗、幼树、根、块茎、茎、柄、枝叶和果实。术语“位点”旨在包括土壤、种子和幼苗以及建立的植被,并且不仅包括杂草可能已经在生长的区域,还包括杂草尚未出苗的区域,以及关于有用植物的作物的耕地区域。“耕地区域”包括作物植物已经在其上生长的土地和旨在耕种此类作物植物的土地。如本文所用,术语“杂草”意指任何不想要的植物,并且因此不仅包括如以下所述的农学上重要的杂草,还包括自生作物植物。
如本文所指,术语“幼苗”,无论单独使用还是以词语组合使用,都意指由种子胚胎发育的幼小植物。
如本文所指,术语“阔叶”,无论单独使用还是以词语诸如“阔叶杂草”使用,均意指双子叶植物(dicot或dicotyledon)——一个用于描述特征在于具有两个子叶的胚胎的被子植物组的术语。
术语‘出苗前施用’(pre-em)意指向杂草出苗到土壤表面以上之前杂草种子或幼苗存在的土壤施用。术语‘出苗后施用’(post-em)意指向出苗到土壤表面以上的杂草的地上或暴露部分施用。术语‘早期出苗后施用’(early post)意指向出苗到土壤表面以上并且在子叶期与二至三叶生长期(或三和四心叶期)之间的杂草的地上或暴露部分施用。
如本文所定义,“全肉汤培养物”或“全细胞培养物”是指含有细胞和培养基两者的液体培养物。如果细菌在板上生长,则可以将细胞收获在水或其他液体中,全培养物。术语“全肉汤培养物”和“全细胞培养物”可互换使用。
如本文所定义,“上清液”是指当细胞在肉汤中生长或从琼脂板收获在另一液体中,并且通过离心、过滤、沉积或本领域熟知的其他方式取出时剩下的液体。
如本文所定义,“滤液”是指来自通过膜的全肉汤培养物的液体。
如本文所定义,“提取物”是指通过溶剂(水、洗涤剂、缓冲剂、有机溶剂)从细胞取出并且通过离心、过滤或另一种方法从细胞分离的液体物质。
如本文所定义,“代谢物”是指微生物发酵的化合物、物质或副产物,或者从具有除草活性的微生物获得的上清液、滤液或提取物。
如本文所定义,“来源于”意指直接从特定来源分离或获得,或者替代性地具有从特定来源分离或获得的物质或生物体的鉴定特征。
如本文所定义,“分离物或分离化合物”基本上不含其他化合物或物质,例如具有至少约20%纯度、优选至少约40%纯度、更优选约60%纯度、甚至更优选约80%纯度、最优选约90%纯度、并且甚至最优选约95%纯度,如通过分析方法所确定,包括但不限于色谱法、电泳法。
如本文所用,术语“烷基”是指具有1至约12个碳原子的单价直链或支链烃基团,包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正己基等。
如本文所用,“取代的烷基”是指还带有一个或多个取代基的烷基,所述取代基选自羟基、烷氧基、巯基、环烷基、取代的环烷基、杂环、取代的杂环、芳基、取代的芳基、杂芳基、取代的杂芳基、芳氧基、取代的芳氧基、卤素、氰基、硝基、氨基、酰胺基、--C(O)H、酰基、氧酰基、羧基、磺酰基、磺酰胺、硫酰基等。
如本文所用,“烯基”是指具有一个或多个碳-碳双键并且具有范围是约2至12个碳原子的直链或支链烃基,并且“取代的烯基”是指还带有一个或多个如以上列出的取代基的烯基。
如本文所用,“炔基”是指具有至少一个碳-碳三键并且具有范围是约2至12个碳原子的直链或支链烃基,并且“取代的炔基”是指还带有一个或多个如以上列出的取代基的炔基。
如本文所用,“芳基”是指具有范围是6至14个碳原子的芳族基团,并且“取代的芳基”是指还带有一个或多个如以上列出的取代基的芳基。
如本文所用,“杂芳基”是指含有一个或多个杂原子(例如,N、O、S等)作为环结构的一部分并且具有范围是3至14个碳原子的芳族环,并且“取代的杂芳基”是指还带有一个或多个如以上列出的取代基的杂芳基。
如本文所用,“烷氧基”是指--O-烷基-部分,其中烷基如上所定义,并且“取代的烷氧基”是指还带有一个或多个如以上列出的取代基的烷氧基。
如本文所用,“硫代烷基”是指--S-烷基-部分,其中烷基如上所定义,并且“取代的硫代烷基”是指还带有一个或多个如以上列出的取代基的硫代烷基。
如本文所用,“环烷基”是指含有在约3至最多8个碳原子范围内的含有环的烷基,并且“取代的环烷基”是指还带有一个或多个如以上列出的取代基的环烷基。
如本文所用,“杂环”是指含有一个或多个杂原子(例如,N、O、S等)作为环结构的一部分并且具有在3至最多14个碳原子范围内的环(即,含有环)基团,并且“取代的杂环”是指还带有一个或多个如以上列出的取代基的杂环基团。
如本文所用,“除草剂安全剂”是添加到除草剂调配物以消除或减少除草剂对于某些作物的植物毒性作用。这些化合物保护作物免受除草剂的损伤,但是通常不妨碍除草剂控制不想要的植被。除草剂安全剂的实例包括但不限于解草酮、解毒喹、苄草隆、解草胺腈、环丙磺酰胺、杀草隆、烯丙酰草胺、迪赛隆(dicyclonon)、增效磷(dietholate)、哌草丹、解草唑、解草啶、解草安、氟草肟、呋喃解草唑、双苯噁唑酸、吡唑解草酯、美芬奈(mephenate)、苯草酮、萘二甲酸酐、解草腈、N-(氨基羰基)-2-甲基苯磺酰胺和N-(氨基羰基)-2-氟苯磺酰胺、1-溴-4-[(氯甲基)磺酰基]苯、2-(二氯甲基)-2-甲基-1,3-二氧戊环(MG 191)、4-(二氯乙酰基)-1-氧杂-4-偶氮螺-[4.5]癸烷(MON 4660)、2,2-二氯-1-(2,2,5-三甲基-3-噁唑烷基)-乙酮以及2-甲氧基-N-[[4-[[(甲基氨基)羰基]氨基]苯基]磺酰基]-苯甲酰胺。值得注意的是增效磷、2,2-二氯-1-(2,2,5-三甲基-3-噁唑烷基)-乙酮和2-甲氧基-N-[[4-[[(甲基氨基)羰基]氨基]苯基]磺酰基]-苯甲酰胺(还称为N-(2-甲氧基苯甲酰基)-4-[(甲基氨基羰基)氨基]苯磺酰胺;CAS#129531-12-0)。特别值得注意的是2-甲氧基-N-[[4-[[(甲基氨基)羰基]氨基]苯基]磺酰基]-苯甲酰胺(还称为N-(2-甲氧基苯甲酰基)-4-[(甲基氨基羰基)氨基]苯磺酰胺;CAS#129531-12-0)。
伯克霍尔德氏菌(Burkholderia)A396(NRRL B-50319)菌株。本文列出的伯克霍尔德氏菌A396菌株是非洋葱伯克霍尔德氏菌(Burkholderia cepacia)复合物、非植物伯克霍尔德氏菌(non-Burkholderia plantari)、非唐菖蒲伯克霍尔德氏菌(non-Burkholderiagladioli)、伯克霍尔德氏菌(Burkholderia sp)并且对于脊椎动物(诸如鸟类、哺乳动物和鱼)不具有致病性。此菌株可以使用本领域已知并且由洛赫(Lorch)等人,1995年所述的程序从土壤样品分离。伯克霍尔德氏菌A396的代谢物的分离、特征和获得方法是本领域已知的,并且可以见于例如美国专利第8,822,193号或美国专利第9,433,218号,两者均通过引用整体并入。
硬脂醇的组成和其在植物生长促进中的使用方法是本领域已知的。更具体地,硬脂醇的各种结构、其使用方法通过引用并入。由R1、R2和R3表示的烃基团可以分别是饱和的或不饱和的基团,优选地饱和基团,并且可以是直链、支链或环状链,优选地直链或支链,特别优选地直链。烃基团中的总碳数可以是奇数或偶数,优选地偶数。R1、R2或R3中的总碳数优选地是50或更少,更优选地12至48,仍然更优选地16至44。在通式(1)中,R1中的碳数优选地是14至22,更优选地14至20,仍然更优选地14至18。由通式(1)表示的化合物中的总碳数优选地是12至48,更优选地16至28,仍然更优选地16至24。所述化合物更优选地是含有总计12至24个碳并且具有一个羟基的化合物,仍然更优选地是含有总计16至22个碳并且具有一个羟基的化合物。
除草化合物
在一个具体实施例中,本发明涉及具有以下结构的除草化合物:
其中X、Y和Z各自独立地是-O、-NR或-S,其中R是H或C1-C10烷基;R1、R2、R3、R4、R5、R6、R7、R8、R11、R12和R13各自独立地是H、烷基、取代的烷基、烷基羧酸、烯基、取代的烯基、炔基、取代的炔基、芳基、取代的芳基、杂芳基、取代的杂芳基、杂环、取代的杂环、环烷基、取代的环烷基、烷氧基、取代的烷氧基、硫代烷基、取代的硫代烷基、羟基、卤素、氨基、酰胺基、羧基、-C(O)H、酰基、氧酰基、氨基甲酸酯、磺酰基、磺酰胺或硫酰基。
在一个具体实施例中,所述组合物可以具有以下结构中的任一种:
本公开的化合物可以化学合成或来源于其他来源,诸如来自生物材料。
本公开的化合物可以在种植作物之前或之后施用、在杂草出苗之前施用(出苗前施用)或杂草出苗之后施用(出苗后施用),并且在出苗后向杂草施用是特别有效的。
上述根据本发明的化合物可以用作未修饰形式的除草剂,如在合成中获得的,但是它们通常使用配制佐剂,诸如载剂、溶剂和表面活性物质以各种方式配制为除草组合物。因此,本发明还涉及一种除草组合物,除配制佐剂以外,其还包含除草有效量的式(I)的化合物。所述调配物可以呈各种物理形式,例如,呈扑撒粉、凝胶、可湿性粉末、水可分散微粒、水可分散片剂、泡腾粒料、乳油、微乳油、水包油乳剂、可流动油状物、水性分散体、油性分散体、悬乳剂、胶囊悬浮剂、可乳化微粒、可溶性液体、水溶性浓缩物(用水或水混溶性有机溶剂作为载剂)、浸渍聚合物膜或例如由《关于植物保护产品的FAO说明书的发展和使用手册(Manual on Development and Use of FAO Specifications forPlant ProtectionProducts)》,第5版,1999已知的其他形式。此类调配物可以直接使用,或者在稀释后使用。稀释可以例如用水、液体肥料、微营养素、生物有机物、油或溶剂进行。
调配物可以例如通过将活性成分与配制佐剂混合,以便获得呈细分固体、微粒、溶液、分散体或乳剂的形式的组合物来制备。活性成分还可以与其他佐剂一起配制,诸如细分固体、矿物油、植物或动物来源的油、植物或动物来源的改性油、有机溶剂、水、表面活性物质或其组合。活性成分还可以容纳在由聚合物组成的非常精细的微胶囊中。微胶囊含有处于多孔载剂中的活性成分。这使得活性成分能够以受控量(例如,缓释)释放到环境中。微胶囊通常具有0.1至500微米的直径。它们含有按胶囊重量计约25重量%至95重量%的量的活性成分。活性成分可以呈整体固体的形式,呈在固体或液体分散体中的细颗粒的形式或呈合适的溶液的形式。封装膜包含例如天然或合成橡胶、纤维素、苯乙烯/丁二烯共聚物、聚丙烯腈、聚丙烯酸酯、聚酯、聚酰胺、聚脲、聚氨酯或化学改性的聚合物和淀粉黄原酸酯或在这方面本领域技术人员已知的其他聚合物。替代性地,可以形成非常精细的微胶囊,其中活性成分呈细分颗粒形式包含在碱性物质的固体基质中,但是微胶囊本身不封装。
适用于制备根据本发明的组合物的配制佐剂本身是已知的。作为液体载剂,可以使用:水、甲苯、二甲苯、石油醚、植物油、丙酮、甲乙酮、环己酮、酸酐、乙腈、苯乙酮、乙酸戊酯、2-丁酮、碳酸亚丁酯、氯苯、环己烷、环己醇、乙酸的烷基酯、二丙酮醇、1,2-二氯丙烷、二乙醇胺、对二乙基苯、二甘醇、松香酸二甘醇酯、二甘醇丁醚、二甘醇***、二甘醇甲醚、N,N-二甲基甲酰胺、二甲基亚砜、1,4-二噁烷、二丙二醇、二丙二醇甲醚、二苯甲酸二丙二醇酯、迪普西托(diproxitol)、烷基吡咯烷酮、乙酸乙酯、2-乙基己醇、碳酸亚乙酯、1,1,1-三氯乙烷、2-庚酮、α-蒎烯、d-柠檬烯、乳酸乙酯、乙二醇、乙二醇丁醚、乙二醇甲醚、γ-丁内酯、甘油、乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、十六烷、己二醇、乙酸异戊酯、乙酸异冰片酯、异辛烷、异佛尔酮、异丙苯、肉豆蔻酸异丙酯、乳酸、月桂胺、异亚丙基丙酮、甲氧基丙醇、甲基异戊酮、甲基异丁基酮、月桂酸甲酯、辛酸甲酯、油酸甲酯、二氯甲烷、间二甲苯、正己烷、正辛胺、十八烷酸、乙酸辛胺、油酸、油胺、邻二甲苯、苯酚、聚乙二醇(PEG400)、丙酸、乳酸丙酯、碳酸亚丙酯、丙二醇、丙二醇甲醚、对二甲苯、甲苯、磷酸三乙酯、三甘醇、二甲苯磺酸、石蜡、矿物油、三氯乙烯、全氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇甲醚、二甘醇甲醚、甲醇、乙醇、异丙醇和较高分子量的醇,诸如戊醇、四氢糠醇、己醇、辛醇、乙二醇、丙二醇、甘油、N-甲基-2-吡咯烷酮等。水通常是用于稀释浓缩物而选择的载剂。合适的固体载剂例如是滑石、二氧化钛、叶蜡石粘土、二氧化硅、凹凸棒粘土、硅藻土、石灰石、碳酸钙、膨润土、钙基蒙脱石、棉籽壳、小麦粉、大豆粉、浮石、木粉、磨碎的核桃壳、木质素以及如例如在CFR 180.1001.(c)&(d)中所述的相似物质。
大量表面活性物质可以有利地用于固体和液体调配物,尤其是用于可以在使用之前用载剂稀释的那些调配物。表面活性物质可以是阴离子、阳离子、非离子或聚合物,并且它们可以用作乳化剂、润湿剂或悬浮剂或用于其他目的。典型的表面活性物质包括例如烷基硫酸盐,诸如月桂基硫酸二乙醇胺;烷基芳基磺酸盐,诸如十二烷基-苯磺酸钙;烷基苯酚/烯化氧加成产物,诸如壬基酚乙氧基化物;醇/烯化氧加成产物,诸如十三烷醇乙氧基化物;肥皂,诸如硬脂酸钠;烷基萘磺酸盐,诸如二丁基萘磺酸钠;磺基琥珀酸盐的二烷基酯,诸如二(2-乙基己基)磺基琥珀酸钠;山梨糖醇酯,诸如山梨糖醇油酸酯;季胺,诸如氯化月桂基三甲基铵,脂肪酸的聚乙二醇酯,诸如聚乙二醇硬脂酸酯;环氧乙烷和环氧丙烷的嵌段共聚物;以及单和二烷基磷酸酯的盐;并且还包括例如在以下中描述的物质:《McCutcheon的洗涤剂和乳化剂年鉴(McCutcheon's Detergents and Emulsifiers Annual)》,MC出版公司,里奇伍德,新泽西州,1981。
通常可以用于农药调配物的另外的佐剂包括结晶抑制剂、粘度改性剂、悬浮剂、染料、抗氧化剂、发泡剂、光吸收剂、混合助剂、消泡剂、配位剂、中和或pH调节物质和缓冲剂、腐蚀抑制剂、香料、润湿剂、吸收增强剂、微营养素、增塑剂、助流剂、润滑剂、分散剂、增稠剂、防冻剂、杀微生物剂以及液体和固体肥料。
根据本发明的组合物可以额外包括添加剂,其包含植物或动物来源的油、矿物油、此类油的烷基酯或此类油和油衍生物的混合物。根据本发明的组合物中的油添加剂的量通常为基于喷雾混合物的0.01%至10%。例如,油添加剂可以在制备喷雾混合物之后以所需浓度添加到喷雾罐中。优选的油添加剂包含矿物油或植物来源的油,例如,菜籽油、橄榄油或葵花籽油;乳化植物油,诸如(罗纳普朗加拿大公司);植物来源的油的烷基酯,例如,甲基衍生物;或动物来源的油,诸如鱼油或牛脂。优选的添加剂含有例如基本上80重量%的鱼油的烷基酯和15重量%的甲基化菜籽油,以及5重量%的常规乳化剂和pH调节剂作为活性组分。尤其优选的油添加剂包含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、棕榈酸和油酸的甲基酯特别重要。这些酯被称为月桂酸甲酯(CAS-111-82-0)、棕榈酸甲酯(CAS-112-39-0)和油酸甲酯(CAS-112-62-9)。优选的脂肪酸甲酯衍生物是2230和2231(科涅斯有限公司(Cognis GmbH))。这些和其他油衍生物还从《除草剂佐剂简编(Compendium of Herbicide Adjuvants)》,第5版,南伊利诺伊斯大学,2000已知。
油添加剂的应用和作用可以通过与表面活性物质诸如非离子、阴离子或阳离子表面活性剂组合来进一步改善。合适的阴离子、非离子和阳离子表面活性剂的实例在WO 97/34485的第7页和第8页上列出。优选的表面活性物质是十二烷基苄基磺酸酯类型的阴离子表面活性剂(尤其是其钙盐),和脂肪醇乙氧化物类型的非离子表面活性剂。特别优选的是乙氧基化C12-C22脂肪醇,其具有5至40的乙氧基化度。可商购获得的表面活性剂的实例是Genapol类型(科莱恩公司)。还优选硅氧烷表面活性剂,尤其是聚烷基环氧改性的七甲基三硅氧烷(其例如作为可商购获得),和全氟表面活性剂。与总添加剂相关的表面活性物质的浓度通常为1重量%至30重量%。由油或矿物油或其衍生物与表面活性剂的混合物组成的油添加剂的实例是Edenor ME (先正达公司,CH)或ActipronC(英国石油有限公司(BP Oil UK Limited),英国)。
如果需要,上述表面活性物质还可能本身用于调配物,也就是说,没有油添加剂。
此外,将有机溶剂添加到油添加剂/表面活性剂混合物可以有助于额外增强作用。合适的溶剂例如是(ESSO)或Aromatic(埃克森公司)。此类溶剂的浓度可以为按总重量的10重量%至80重量%。与溶剂一起存在于混合物中的油添加剂在例如美国专利第4,834,908号中描述。本文公开的可商购获得的油添加剂被称为(巴斯夫公司)。根据本发明优选的另外的油添加剂是(加拿大先正达作物保护有限公司)。
除以上列出的油添加剂以外,出于增强根据本发明的组合物的作用的目的,还可以将烷基吡咯烷酮的调配物(例如,)添加到喷雾混合物。还可以使用合成晶格(例如,聚丙烯酰胺、聚乙烯化合物或聚1-对孟烯)的调配物(例如,或)。还可以将含有丙酸的溶液(例如,Eurogkem)作为作用增强剂添加到喷雾混合物。
除草组合物通常包含0.1重量%至99重量%,尤其是0.1重量%至95重量%的式(I)的化合物以及1重量%至99.9重量%的配制佐剂,其优选包含0重量%至25重量%的表面活性物质。虽然商业产品优选被配制为浓缩物,但是终端用户通常采用稀释调配物。
在甚至更具体的实施例中,以上化合物中的任一种可以来自天然材料或从商业来源获得或分离或通过化学合成得到的化合物,例如参见美国专利申请第U.S.2008/0096879A1号,其内容特通过引用整体并入。天然来源包括但不限于微生物、海藻和海绵。在更具体的实施例中,微生物包括诸如伯克霍尔德氏菌的物种。更具体的实施例包括伯克霍尔德氏菌A396(NRRL B-50319)。
本公开的化合物可以作为一种或多种立体异构体存在。各种立体异构体包括对映体、非对映体、阻转异构体和几何异构体。立体异构体是组成相同但是空间中其原子的排列不同的异构体,并且包括对映体、非对映体、顺-反异构体(还称为几何异构体)和阻转异构体。阻转异构体由绕单键进行受限旋转产生,其中旋转势垒足够高来允许异构体物质的分离。本领域技术人员将理解,一种立体异构体在相对于其他立体异构体富集时或在与其他立体异构体分离时可以更具活性和/或可以表现出有益作用。另外,技术人员知道如何分离、富集和/或选择性制备所述立体异构体。本公开的化合物可以作为立体异构体的混合物、个体立体异构体或作为光学活性形式存在。
以上化合物可以作为除草剂使用。用以上列出的组合物处理植物和植物部分的方法可以直接进行或通过例如浸渍、淋水、灌施、喷雾、蒸发、雾化、散射、喷涂、注射来使所述组合物作用于其周围环境、栖息地或储存空间上来进行。
组合物可以使用本领域已知的方法施用。具体地,这些组合物可以施用到植物或植物部分。在本发明上下文中,植物被理解为意指所有的植物和植物群体,诸如想要的和不想要的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以是可以通过以下方法获得的植物:常规植物育种和优化方法,或生物技术和基因工程方法或这些方法的组合,包括转基因植物并且包括受植物育种者权利保护或不受保护的植物品种。植物部分被理解为意指植物在地面以上和以下的所有部分和器官,诸如芽、叶、花和根,可以提及的实例为叶、针叶、柄、茎、花、子实体、果实、种子、根、块茎和根茎。植物部分还包括收获的物质,以及营养和生殖传播物质,例如插条、块茎、根茎、分枝和种子。
本公开的化合物通常可用作组合物(即,调配物)中的除草活性成分,其中至少一种额外组分选自由以下组成的群组:表面活性剂、固体稀释剂和液体稀释剂,其充当载剂。调配物或组合物成分被选择来与活性成分的物理特性、施用模式和环境因素(诸如土壤类型、湿度和温度)一致。
可用的调配物包括液体和固体组合物两者。液体组合物包括溶液(包括可乳化浓缩物)、悬浮剂、乳剂(包括微乳剂、水包油乳剂、可流动浓缩物和/或悬浮剂)等,其任选地可以增稠为凝胶。水性液体组合物的一般类型为可溶性浓缩物、悬浮剂浓缩物、胶囊悬浮剂、浓缩乳剂、微乳剂、水包油乳剂、可流动浓缩物和悬乳剂。非水性液体组合物的一般类型为可乳化浓缩物、微可乳化浓缩物、可分散浓缩物和油分散体。
固体组合物的一般类型为粉尘、粉末、微粒、粒料、球粒、锭剂、片剂、填充膜(包括种子包衣)等,其可以是水可分散的(“可润湿的”)或水可溶的。由成膜溶液或可流动悬浮剂形成的膜和包衣特别可用于种子处理。活性成分可以(微)囊装并且进一步形成悬浮剂或固体调配物;替代性地,活性成分的整个调配物可以囊装(或“包覆”)。囊装可以控制或延迟活性成分的释放。可乳化微粒结合了可乳化浓缩物调配物和干燥粒状调配物两者的优点。高浓度组合物主要用作用于进一步调配的中间体。
可喷雾调配物通常在喷雾之前在合适的介质中延伸。此类液体和固体调配物被调配为易于稀释在喷雾介质中,通常为水,但是有时为另一种合适的介质,像芳族烃或石蜡烃或植物油。喷雾体积可在约一至几千升/公顷的范围内,但是更通常在约十至几百升/公顷的范围内。可喷雾调配物可以与水或另一种合适的介质进行罐混合,以用于通过空中或地面施用进行叶处理或用于施用到植物的生长介质。液体和干燥调配物可以直接计量到滴灌***中或在种植期间计量到犁沟中。
调配物通常含有在以下适当范围内的有效量的活性成分、稀释剂和表面活性剂,所述适当范围总和为100重量%。
用于本文公开的组合物和方法的以上列出的物质可以任何方式调配。非限制性调配物实例包括但不限于可乳化浓缩物(EC)、可润湿粉末(WP)、可溶性液体(SL)、气溶胶、超低体积浓缩物溶液(ULV)、可溶性粉末(SP)、微胶囊、水分散微粒、可流动物(FL)、微乳剂(ME)、纳米乳剂(NE)以及种子处理物等。在本文所述的任何调配物中,活性成分的百分比在0.01%至99.99%的范围内,并且包括其任何和所有的增量变化。
组合物可以额外包含表面活性剂以用于活性成分的乳化、吸收、粘附、分散、润湿、扩散、融合、崩解控制、稳定化,和改善流动性或防锈性。在具体实施例中,表面活性剂是非植物毒性的非离子表面活性剂,其属于EPA惰性成份列表4B。在另一个具体实施例中,非离子表面活性剂是聚氧乙烯(20)单月桂酸酯。表面活性剂的浓度范围可以在总调配物的0.1%-35%之间,或者范围是5%-25%。分散剂和乳化剂(诸如非离子、阴离子、两性和阳离子分散剂和乳化剂)的选择和所采用的量是由组合物的性质和所述药剂促进组合物分散的能力来决定。
固体稀释剂包括例如粘土,诸如膨润土、蒙脱石、凹凸棒石和高岭土;石膏、纤维素、二氧化钛、氧化锌、淀粉、糊精、糖(例如,乳糖、蔗糖)、二氧化硅、滑石、云母、硅藻土、尿素、碳酸钙、碳酸钠和碳酸氢钠以及硫酸钠。典型的固体稀释剂在以下描述:沃特金斯(Watkins)等人,《杀虫剂粉尘稀释剂和载剂手册(Handbook of Insecticide DustDiluents and Carriers)》,第2版,多兰图书(Dorland Books),考德威尔,新泽西州。
液体稀释剂包括例如水、N,N-二甲基烷烃胺(例如,N,N-二甲基甲酰胺)、柠檬烯、二甲基亚砜、N-烷基吡咯烷酮(例如,N-甲基吡咯烷酮)、磷酸烷基酯(例如,磷酸三乙酯)、乙二醇、三乙二醇、丙二醇、二丙二醇、聚丙二醇、碳酸亚丙酯、碳酸亚丁酯、石蜡(例如,矿物白油、正链烷烃、异链烷烃)、烷基苯、烷基萘、甘油、三乙酸甘油酯、山梨糖醇、芳族烃、脱芳构化脂族、烷基苯、烷基萘、酮(诸如环己酮、2-庚酮、异佛尔酮和4-羟基-4-甲基-2-戊酮)、乙酸酯(诸如乙酸异戊酯、乙酸己酯、乙酸庚酯、乙酸辛酯、乙酸壬酯、乙酸十三烷基酯和乙酸异冰片酯)、其他酯诸如烷基化乳酸酯、二元酸酯、烷基和芳基苯甲酸酯和丁内酯以及醇,其可以是直链的、支链的、饱和的或不饱和的,诸如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己醇、2-乙基己醇、正辛醇、癸醇、异癸醇、异十八烷醇、鲸蜡醇、月桂醇、十三烷醇、油醇、环己醇、四氢糠醇、二丙酮醇、甲酚和苯甲醇。液体稀释剂还包括饱和与不饱和脂肪酸的甘油酯(通常为C6-C22),诸如植物种子和果实油(例如,橄榄、蓖麻、亚麻籽、芝麻、玉米(苞米)、花生、向日葵、葡萄籽、红花、棉籽、大豆、油菜籽、椰子和棕榈仁的油)、动物来源的脂肪(例如,牛脂、猪脂、猪油、鱼肝油、鱼油)及其混合物。液体稀释剂还包括烷基化脂肪酸(例如,甲基化、乙基化、丁基化),其中脂肪酸可以通过植物和动物来源的甘油酯的水解获得并且可以通过蒸馏纯化。典型的液体稀释剂在以下中描述:马斯登(Marsden),《溶剂指南(Solvents Guide)》,第2版,Interscience,纽约,1950。
本公开的固体和液体组合物常常包括一种或多种表面活性剂。在添加到液体时,表面活性剂(还称为“表面活性助剂”)通常会改变,最常见地降低液体的表面张力。根据表面活性剂分子中亲水和亲脂基团的性质,表面活性剂可以用作润湿剂、分散剂、乳化剂或脱泡沫剂。
表面活性剂可以分为非离子、阴离子或阳离子。可用于本发明的组合物的非离子表面活性剂包括但不限于:醇烷氧基化物,诸如基于天然醇和合成醇(其可以是支链或直链)并且由醇和环氧乙烷、环氧丙烷、环氧丁烷或其混合物制备的醇烷氧基化物;胺乙氧基化物、烷醇酰胺和乙氧基化烷醇酰胺;烷氧基化甘油三酯,诸如乙氧基化大豆油、蓖麻油和菜籽油;烷基酚烷氧基化物,诸如辛基酚乙氧基化物、壬基酚乙氧基化物、二壬基酚乙氧基化物和十二烷基酚乙氧基化物(由酚和环氧乙烷、环氧丙烷、环氧丁烷或其混合物制备);由环氧乙烷或环氧丙烷制备的嵌段共聚物和其中端嵌段由环氧丙烷制备的反向嵌段共聚物;乙氧基化脂肪酸;乙氧基化脂肪酯和油;乙氧基化甲酯;乙氧基化三苯乙烯基酚(包括由环氧乙烷、环氧丙烷、环氧丁烷或其混合物制备的那些);脂肪酸酯、甘油酯、羊毛脂基衍生物、聚乙氧基酯诸如聚乙氧基化脱水山梨糖醇脂肪酸酯、聚乙氧基化山梨糖醇脂肪酸酯和聚乙氧基化甘油脂肪酸酯;其他脱水山梨糖醇衍生物诸如脱水山梨糖醇酯;聚合物表面活性剂,诸如无规共聚物、嵌段共聚物、醇酸peg(聚乙二醇)树脂、接枝或梳形聚合物和星形聚合物;聚乙二醇(peg);聚乙二醇脂肪酸酯;硅氧烷基表面活性剂;以及糖衍生物诸如蔗糖酯、烷基多苷和烷基多糖。
阴离子表面活性剂包括但不限于:烷基芳基磺酸和其盐;羧化醇或烷基酚乙氧基化物;磺酸二苯酯衍生物;木质素和木质素衍生物,诸如木质素磺酸盐;马来酸或琥珀酸或其酸酐;烯烃磺酸盐;磷酸酯,诸如醇烷氧基化物的磷酸酯、烷基酚烷氧基化物的磷酸酯和苯乙烯基酚乙氧基化物的磷酸酯;蛋白质基表面活性剂;肌氨酸衍生物;苯乙烯基酚醚硫酸盐;油和脂肪酸的硫酸盐和磺酸盐;乙氧基化烷基酚的硫酸盐和磺酸盐;醇的硫酸盐;乙氧基化醇的硫酸盐;胺和酰胺的磺酸盐,诸如N,N-烷基牛磺酸盐;苯、枯烯、甲苯、二甲苯和十二烷基和十三烷基苯的磺酸盐;缩合萘的磺酸盐;萘和烷基萘的磺酸盐;分馏石油的磺酸盐;磺基琥珀酰胺酸盐(sulfosuccinamates);以及磺基琥珀酸盐和其衍生物,诸如磺基琥珀酸二烷基酯盐。
阳离子表面活性剂包括但不限于:酰胺和乙氧基化酰胺;胺,诸如N-烷基丙烷二胺、三丙烯三胺和二丙烯四胺,以及乙氧基化胺、乙氧基化二胺和丙氧基化胺(由胺和环氧乙烷、环氧丙烷、环氧丁烷或其混合物制备);胺盐,诸如胺乙酸盐和二胺盐;季铵盐,诸如季盐、乙氧基化季盐和二季盐;以及胺氧化物,诸如烷基二甲基胺氧化物和双(2-羟乙基)-烷基胺氧化物。
另外,本发明组合物是非离子和阴离子表面活性剂的混合物或非离子和阳离子表面活性剂的混合物。非离子、阴离子和阳离子表面活性剂及其推荐用途在各种公布的参考文献中公开,包括《麦卡琴的乳化剂和洗涤剂(McCutcheon's Emulsifiers andDetergents)》,美国和国际年度版,由麦卡琴(McCutcheon)部门,糖果制造商出版公司(Manufacturing Confectioner Publishing Co.)出版;西斯利(Sisely)和伍德(Wood),《表面活性剂大全(Encyclopedia of Surface Active Agents)》,化学出版有限公司,纽约,1964;以及A.S.戴维森(A.S.Davidson)和B.米尔维斯基(B.Milwidsky),《合成洗涤剂(Synthetic Detergents)》,第7版,约翰威立父子(John Wiley and Sons),纽约,1987。
本公开的组合物还可以含有配制助剂和添加剂,作为配制辅料(其中的一些可以被认为还充当固体稀释剂、液体稀释剂或表面活性剂)为技术人员已知。此类配制助剂和添加剂可以控制:pH(缓冲剂)、处理期间的发泡(消泡剂,诸如聚有机硅氧烷)、活性成分的沉积(悬浮剂)、粘度(触变增稠剂)、容器内微生物生长(抗菌剂)、产物冷冻(防冻剂)、颜色(染料/颜料分散体)、洗除(成膜剂或粘结剂)、蒸发(蒸发阻滞剂)以及其他配制属性。成膜剂包括例如聚乙酸乙烯酯、聚乙酸乙烯酯共聚物、聚乙烯吡咯烷酮-乙酸乙烯酯共聚物、聚乙烯醇、聚乙烯醇共聚物和蜡。配制助剂和添加剂的实例包括以下中列出的那些:《麦卡琴第2卷:功能材料(McCutcheon's Volume 2:Functional Materials)》,北美和国际年鉴版,由麦卡琴部门,糖果制造商出版公司出版;以及PCT公开WO 03/024222。
如以上列出的组合物还包含稳定剂,其使生物杀虫剂组合物稳定化来抵抗物理分离和由于日照导致的活性损失。此稳定剂可以是苯甲酸盐或木质素磺酸盐。
本文公开的除草组合物可以液体或固体形式作为出苗前或出苗后调配物施用。
对于出苗前干燥调配物,载剂的微粒大小通常为1-2mm(直径),但是根据所需的地面覆盖,微粒可以更小或更大。微粒可以含有多孔或无孔颗粒。
出于出苗后调配物,所用的调配物组分可以含有层状粘土、凹凸棒粘土和相似的溶胀粘土、增稠剂诸如黄原胶、***胶和其他多糖增稠剂以及分散稳定剂诸如非离子表面活性剂(例如聚氧乙烯(20)单月桂酸酯)。
此外,组合物可以与种子涂覆剂组合使用。此类种子涂覆剂可以包括但不限于乙二醇、羧甲基纤维素、甲基纤维素、聚乙二醇、壳聚糖、羧甲基壳聚糖、泥炭藓、树脂和蜡。组合物可以使用本领域已知的方法施用。具体地,这些组合物可以施用到植物或植物部分和其周围。在本发明上下文中,植物被理解为意指所有的植物和植物群体,诸如想要的和不想要的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以是可以通过以下方法获得的植物:常规植物育种和优化方法,或生物技术和基因工程方法或这些方法的组合,包括转基因植物并且包括受植物育种者权利保护或不受保护的植物品种。植物包括植物在地面以上和以下的所有部分和器官,诸如芽、叶、花和根,可以提及的实例为叶、针叶、柄、茎、花、子实体、果实、种子、根、块茎和根茎。植物包括但不限于收获的物质,以及营养和生殖传播物质,例如插条、块茎、根茎、分枝和种子。
本公开的化合物的除草有效量由多种因素决定。这些因素包括:所选择的调配物、施用方法、存在的植被的量和类型、生长条件等。一般而言,本公开的化合物的除草有效量为约0.005至约20kg/ha。在一些实施例中,范围是约0.01至约1kg/ha。本领域技术人员可以容易地确定所需水平的杂草控制所需要的除草有效量。
可以根据本公开处理的遗传修饰的植物品种包括对于一种或多种生物胁迫(害虫,诸如线虫、昆虫、螨虫、真菌等)或非生物胁迫(干旱、低温、土壤盐分等)具有抗性的那些,或具有其他希望特征的那些。植物可以进行遗传修饰以表现出例如除草剂耐受性、昆虫抗性、改变的油特征或干旱耐受性的特性。可用的遗传修饰的植物含有单基因转化事件或转化事件的组合。遗传修饰的额外信息可以从例如由美国农业部提供的公共可用数据库获得。
用本公开的化合物处理遗传修饰的植物可以产生超加成作用或协同作用。例如,施用率的降低、活性谱的拓宽、对生物/非生物胁迫的耐受性的增加或储存稳定性的增强可能大于在遗传修饰的植物上施用本公开的化合物的仅简单的加成作用。
本公开的化合物还可以与一种或多种其他生物活性化合物或剂混合,包括除草剂、除草剂安全剂、杀真菌剂、杀虫剂、杀线虫剂、杀菌剂、杀螨剂、生长调节剂(诸如昆虫蜕皮抑制剂和生根刺激剂)、化学不育剂、化学信息素、驱避剂、引诱剂、信息素、促摄食物质、植物营养素、其他生物活性化合物或昆虫病原菌、病毒或真菌,以形成多组分杀虫剂,从而产生甚至更宽谱的农业保护。本公开的化合物与其他除草剂的混合物可以拓宽针对额外的杂草物种的活性谱,并且抑制任何抗性生物类型的增殖。
组合物还可以包含一种或多种额外除草剂。这些包括但不限于生物除草剂和/或化学除草剂。生物除草剂可以选自由以下组成的群组:丁香、肉桂、柠檬草、柑橘油、橙皮油、腾毒素、康奈西斯汀、AAL-毒素、纤精酮、萨托明、假蒟亭碱、稻壳酮B、高粱酮、壬酸、辛酸、癸酸、阿斯科拉毒素和阿斯科拉毒素阿格来康。化学除草剂可以包括但不限于三嗪、三嗪酮、脲、酰胺、二苯醚、***啉酮、联吡啶鎓、广灭灵、4-HPPD抑制剂、PDS抑制剂、咪唑啉酮、磺酰脲、嘧啶基(硫代)苯甲酸酯、***并嘧啶、甘氨酸、次膦酸、二硝基苯酚、环己二酮、芳氧基苯氧基丙酸酯、磺草灵、硫代氨基甲酸酯、二硝基苯胺、氨基甲酸酯、氯乙酰胺、烷基嗪、异噁酰草胺、吡啶-羧酸、苯甲酸、喹啉羧酸、苯氧基羧酸和MSMA。组合物还可以包含一种或多种杀虫剂。
为了拓宽作用谱并实现协同作用,式I的化合物可以与大量代表性的其他除草或生长调节活性成分组混合,然后同时施用。混合物的合适组分是例如1,2,4-噻二唑、1,3,4-噻二唑、酰胺、氨基磷酸及其衍生物、氨基***、酸酐、(杂)芳氧基链烷酸及其衍生物、苯甲酸和其衍生物、苯并噻二嗪酮(benzothiadiazinone)、2-芳酰基-1,3-环己烷二酮、2-杂酰基-1,3-环己烷二酮、杂芳基芳基酮、苄基异噁唑烷酮、间-CF3-苯基衍生物、氨基甲酸酯、喹啉羧酸和其衍生物、氯乙酰苯胺、环己烯酮肟醚衍生物、二嗪、二氯丙酸和其衍生物、二氢苯并呋喃、二氢呋喃-3-酮、二硝基苯胺、二硝基苯酚、二苯醚、二吡啶、卤代羧酸和其衍生物、尿素、3-苯基尿嘧啶、咪唑、咪唑啉酮、N-苯基-3,4,5,6-四氢邻苯二甲酰亚胺、噁二唑、环氧乙烷、苯酚、芳氧基和杂芳氧基苯氧基丙酸酯、苯乙酸和其衍生物、2-苯基丙酸和其衍生物、吡唑、苯基吡唑、哒嗪、吡啶羧酸和其衍生物、嘧啶基醚、磺酰胺、磺酰脲、三嗪、三嗪酮、***啉酮、***甲酰胺、尿嘧啶、苯基吡唑啉和异噁唑啉和其衍生物。
在具体实施例中,组合物和除草化合物来源于伯克霍尔德氏菌A396(NRRL B-50319)菌株。
物质和组合物还可以用于在单子叶、苔草或双子叶杂草的出苗前或出苗后调配物中调控出苗。在具体实施例中,杂草可以是长芒苋、西部苋、藜、苘麻、向日葵、豚草(Ambrosia artemesifolia)、反枝苋、田旋花、田芥菜(Brassica kaber)、药用蒲公英、龙葵、圆叶锦葵(Malva neglect)、金狗尾草(Setaria lutescens)、旱雀麦、早熟禾、草地早熟禾、长芒苋(Palmer amaranth)、多年生黑麦草(Lolium perenne L.)变种Pace、高羊茅(Festuca arundinaceae Schreb.)变种Aztec II、Anthem II、LS1100、稗草和/或莴苣。
除草协同作用
在一个实施例中,FR901464和/或思普力西欧他汀C的除草组合物在通过旋转和/或罐混合与硬脂醇一起施用时可以表现出除草协同作用。
硬脂醇可以具有下式:
其中R1表示C10至C22烃基团,R2表示氢原子、羟基或C1至C24烃基团,并且R3表示氢原子或C1至C24烃基团。
除草协同作用可以通过本领域已知的方法测量。例如,使用Colby公式,其中当比率大于1时,它指示协同作用。
意外且出乎意料的是,硬脂醇与FR901464/思普力西欧他汀C之间具有协同作用,因为已知硬脂醇促进植物生长,而在与FR901464/思普力西欧他汀C组合时,组合表现出增强的除草活性。
实例
以上列出的组合物和方法将在以下非限制性实例中进一步示出。实例仅示出示例性实施例,并且不限制关于本文引用的材料、条件、重量比、处理参数等要求保护的本发明。
实例1:从热灭活的伯克霍尔德氏菌A396(NRRL B-50319)分离活性组分和物质。
如以上指出的,除草组合物可以化学合成或来源于生物有机物。在此,提取来源于100L发酵伯克霍尔德氏菌(A396)的培养肉汤以得到粗提取物。然后使用反相C18真空液相色谱法(H2O/CH3OH)对粗提取物进行分级以得到5个级分。然后,使用籽粒苋(***苋(Burgundy amaranth))进行的植物测定筛选这些级分的除草活性。然后,使活性级分(F3&F4)经受反相HPLC来得到纯化合物,随后纯化合物在上述生物测定中进行测试以确定/鉴定活性化合物。在1.3和0.65μg/mL下测试分离的化合物,并且结果显示两种化合物的抑制性控制。为了确认化合物的身份,记录额外的光谱数据,诸如LC-MS和NMR。基于数据的详细分析,鉴定两种化合物为FR 901464(MW 507)和思普力西欧他汀C(MW 519)。注意到,不同的发酵方法将产生不同(或没有)量的一种或多种以下化合物,一些根本不产生。
实例2:FR901464和思普力西欧他汀C针对***苋的除草生物测定。
***苋(籽粒苋)植物在温室中在含有植物生长混合物与缓释肥的2.5cm方形盆中生长至3-4叶期。然后使用适配有8001喷嘴的研究室履带式喷雾器并且以20gal/A的载剂体积施用进行处理。对阴性对照喷水。将盆在喷雾之后通过处理分组并随机化,并且置于25℃和50%RH的生长室中,并且按需要浇水。在施用之后6天评估植物的视觉损伤和鲜重。使表1中的数据经受ANOVA,并且使用Tukey法以95%置信区间分离平均值。
表1
实例3:FR901464和思普力西欧他汀C针对长芒苋的除草生物测定。
在不同浓度下针对长芒苋(Amaranthus palmeri,Palmer amaranth)测试分离的化合物FR 901464(RT 23)和思普力西欧他汀C(MW 519,RT 36)。长芒苋植物在温室中在含有植物生长混合物与缓释肥的2.5cm方形盆中生长至3-4叶期。然后使用适配有8001喷嘴的研究室履带式喷雾器并且以20gal/A的载剂体积施用进行处理。对阴性对照(UTC=未经处理对照)喷水。将盆在喷雾之后通过处理分组并随机化,并且置于外面的阳光下,并且按需要浇水。在施用之后6天评估植物的视觉损伤和鲜重。使数据经受ANOVA,并且使用Tukey法以95%置信区间分离平均值。图1至10代表所得的数据。简而言之,所述分子是有效的除草化合物。
实例4:在与硬脂醇(HAVEN)一起施用时FR901464和/或思普力西欧他汀C(MBI-014)的除草协同作用。
长芒苋(Amaranthus palmeri,Palmer amaranth)植物在温室中在含有植物生长混合物与缓释肥的2.5cm方形盆中生长至3-4叶期。然后进行处理,使用适配有8002喷嘴的研究室履带式喷雾器作为叶喷雾或作为20mL/盆浸液倒在土壤表面上。将MBI-014以3磅/英亩(lb/A)的比率施用并且在40加仑/英亩(GPA)的载剂体积下喷雾1%v/v有机硅表面活性剂;在1GPA下施用没有佐剂的Haven,并且稀释到水中以达到100GPA的最终喷雾体积;对阴性对照喷水。在将两种产品喷雾到植物上时,首先施用MBI-014,使其干燥,然后施用Haven的喷雾。重复进行处理5次。将盆在喷雾之后通过处理分组并随机化,并且置于25℃和50%RH的温室中,并且按需要浇水。在施用之后6天评估植物的视觉损伤。使数据经受ANOVA,并且使用Fisher LSD法以90%置信区间分离平均值。
结果:与仅施用MBI-014(88%)相比,在将MBI-014施用到叶之后将Haven施用到叶不增加植物中除草症状的严重性(74%)。然而,与仅用浸液处理植物(46%)相比,在将MBI-014作为浸液施用并且将Haven施用到叶时,植物损伤显著增加(80%)。使用Colby协同作用公式,其中1的值代表中性状态,低于1代表拮抗作用,而高于1代表协同作用,浸液+喷雾处理产生1.38的分数,落在协同作用的类别中。因为本公开已经确定Haven的叶施用可以增加植物的蒸腾速率,所以此协同作功效的原因似乎在于:由于Haven使植物蒸腾作用增强,致使植物从土壤吸收更多的MBI-014到根中并且上升到植物维管***中,从而将受影响植物的更大面积暴露于更大量的除草剂。
生物材料的保藏。以下生物材料已经根据布达佩斯条约在美国农业研究培养物保藏中心(NRRL),1815N.皮奥瑞亚,大学街,Ill.61604保藏,并且给与以下保藏号:
所述菌株根据以下条件保藏:在本申请未决期间,由美国专利和商标局局长按37C.F.R.§1.14和35U.S.C.§122的授权确定谁可以访问保藏物。保藏物表示所保藏菌株的基本上纯的培养物。可以根据国外专利法的要求在提交本申请的相应部分或其后续申请的国家中获得所述保藏物。然而,应理解,保藏物的获取并不构成在减损政府行为授予的专利权的情况下实践本发明的许可。
预期,此说明书中讨论的任何实施例可以针对本发明的任何方法、试剂盒、试剂或组合物实施,并且反之亦然。此外,本发明的组合物可以用于实现本发明的方法。
应理解,本文所述的具体实施例以例示的方式示出并且不限制本发明。可以在不脱离本发明的范围的情况下在各种实施例中采用本发明的基本特征。本领域技术人员将认识到或能够仅使用常规实验确定本文所描述的具体程序的多种等效物。此类等效物被认为在本发明的范围内并且由权利要求书覆盖。
当在权利要求书和/或说明书中连同术语“包含”一起使用时,使用的措辞“一个”或“一种”可意味“一个”,但它也符合“一个或多个”、“至少一个”及“一个或多于一个”的含义。在权利要求书中使用术语“或”用于意指“和/或”,除非明确地指示是指仅替代物或替代物是相互排斥的,虽然本公开支持是指仅替代物和“和/或”的定义。在整个本申请中,术语“约”用于指示值包括装置、用于测定所述值的方法的误差的固有变化,或研究受试者中存在的变化。
如在此说明书和权利要求中所用,词语“包含(comprising)”(和任何形式的包含,诸如“包含(comprise)”和“包含(comprises)”)、“具有(having)”(和任何形式的具有,诸如“具有(have)”和“具有(has)”)、“包括”(和任何形式的包括,诸如“包括(includes)”和“包括(include)”)或“含有(containing)”(和任何形式的含有,诸如“含有(contains)”和“含有(contain)”)是包括端值在内或开放式的,并且不排除额外的未列举的元素或方法步骤。
如本文所用,术语“或其组合”是指术语之前列出项目的所有排列和组合。例如,“A、B、C或其组合”旨在包括以下中的至少一种:A、B、C、AB、AC、BC或ABC,并且如果顺序在特定环境中是重要的,还包括BA、CA、CB、CBA、BCA、ACB、BAC或CAB。继续此实例,明确地包括含有一种或多种项目或术语的重复的组合,诸如BB、AAA、AB、BBC、AAABCCCC、CBBAAA、CABABB等等。本领域技术人员将理解,通常对于任何组合中的项目或术语的数量没有限制,除非根据上下文明显相反。
可以根据本公开实现本文公开和要求保护的所有组合物和/或方法并且在不进行过多实验的情况下执行。尽管本发明的组合物和方法已经根据优选实施例加以描述,但对本领域技术人员显而易见的是在不偏离本发明的概念、精神和范围的情况下,可以对本文所述的组合物和/或方法以及本文所述方法的步骤或步骤的顺序进行变更。对本领域技术人员显而易见的所有此类相似的替代和修改被认为在如由所附权利要求书限定的本发明的精神、范围和概念内。
Claims (10)
1.一种用于抑制单子叶、苔草或双子叶杂草的出苗或生长的方法,其包含:
施用以下的组合物:
a)有效量的FR901464;和
b)载剂、稀释剂、表面活性剂、佐剂中的至少一种;
以抑制所述杂草的生长。
2.根据权利要求1所述的方法,其中所述单子叶、苔草或双子叶杂草选自由以下组成的群组:籽粒苋、藜、苘麻、向日葵、豚草、反枝苋、田旋花、田芥菜、药用蒲公英、龙葵、圆叶锦葵、金狗尾草、旱雀麦、早熟禾、草地早熟禾、长芒苋、多年生黑麦草变种Pace、高羊茅变种Aztec II、Anthem II、LS1100、稗草和莴苣。
3.根据权利要求1所述的方法,其中所述组合物还包含另一种除草化合物或杀虫剂化合物。
4.根据权利要求3所述的方法,其中所述另一种除草化合物包含丁香、肉桂、柠檬草、柑橘油、橙皮油、腾毒素、康奈西斯汀、AAL-毒素、纤精酮、萨托明、假蒟亭碱、稻壳酮B、高粱酮、阿斯科拉毒素、阿斯科拉毒素阿格来康、氟吡草腙和其盐、麦草畏和其盐、苯唑草酮、环磺酮、S-异丙甲草胺、阿特拉津、甲基磺草酮、氟嘧磺隆、2,4-二氯苯氧基乙酸、烟嘧磺隆、噻吩磺隆、赛克津、禾草灵、吡氟禾草灵、精噁唑禾草灵、乙氧氟草醚、砜嘧磺隆、2甲4氯丙酸和二氯喹啉酸、禾草丹、广灭灵、氰氟草酯、敌稗、苄嘧磺隆、五氟磺草胺、绿草定、咪草烟、氯吡嘧磺隆、二甲戊乐灵、双草醚、唑酮草酯、灭草松钠/三氟羧草醚钠、草甘膦、草丁膦、硬脂醇或嘧苯胺磺隆。
5.根据权利要求1所述的方法,其中所述FR90146是从伯克霍尔德氏菌A396(NRRL B-50319)分离。
6.根据权利要求1所述的方法,其中所述组合物还包含FR90146的盐或立体异构体。
7.一种协同除草组合物,其包含(a)化合物FR90146;和(b)另一种除草剂,其选自由以下组成的群组:丁香、肉桂、柠檬草、柑橘油、橙皮油、腾毒素、康奈西斯汀、AAL-毒素、纤精酮、萨托明、假蒟亭碱、稻壳酮B、高粱酮、阿斯科拉毒素、阿斯科拉毒素阿格来康、氟吡草腙和其盐、麦草畏和其盐、苯唑草酮、环磺酮、S-异丙甲草胺、阿特拉津、甲基磺草酮、氟嘧磺隆、2,4-二氯苯氧基乙酸、烟嘧磺隆、噻吩磺隆、赛克津、禾草灵、吡氟禾草灵、精噁唑禾草灵、乙氧氟草醚、砜嘧磺隆、2甲4氯丙酸和二氯喹啉酸、禾草丹、广灭灵、氰氟草酯、敌稗、苄嘧磺隆、五氟磺草胺、绿草定、咪草烟、氯吡嘧磺隆、二甲戊乐灵、双草醚、唑酮草酯、灭草松钠/三氟羧草醚钠、草甘膦、草丁膦、硬脂醇和嘧苯胺磺隆。
8.一种用于抑制单子叶、苔草或双子叶杂草的出苗或生长的方法,其包含:
向所述杂草施用有效抑制所述杂草的出苗的根据权利要求7所述的协同组合物。
9.根据权利要求8所述的方法,其中所述施用方法是通过罐混合进行的。
10.根据权利要求9所述的方法,其中所述方法是通过旋转进行的。
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CN117603887A (zh) * | 2024-01-19 | 2024-02-27 | 中国科学院南京土壤研究所 | 一种低温降解除草剂合成菌群及其应用 |
CN117603887B (zh) * | 2024-01-19 | 2024-03-22 | 中国科学院南京土壤研究所 | 一种低温降解除草剂合成菌群及其应用 |
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BR112020002697A2 (pt) | 2020-07-28 |
CN111246740A (zh) | 2020-06-05 |
JP2023071990A (ja) | 2023-05-23 |
WO2019051029A3 (en) | 2019-05-02 |
US11206832B2 (en) | 2021-12-28 |
CN111246740B (zh) | 2022-06-10 |
CA3072096A1 (en) | 2019-03-14 |
JP2020533312A (ja) | 2020-11-19 |
US20200214297A1 (en) | 2020-07-09 |
EP3678488A4 (en) | 2021-06-02 |
JP7245231B2 (ja) | 2023-03-23 |
US20220079156A1 (en) | 2022-03-17 |
WO2019051029A2 (en) | 2019-03-14 |
EP3678488A2 (en) | 2020-07-15 |
MX2020002634A (es) | 2020-07-13 |
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