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CN1155540A - 具有除草活性的硫代氨基甲酰基四唑啉酮类化合物 - Google Patents

具有除草活性的硫代氨基甲酰基四唑啉酮类化合物 Download PDF

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CN1155540A
CN1155540A CN96111754A CN96111754A CN1155540A CN 1155540 A CN1155540 A CN 1155540A CN 96111754 A CN96111754 A CN 96111754A CN 96111754 A CN96111754 A CN 96111754A CN 1155540 A CN1155540 A CN 1155540A
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五岛敏男
伊藤整志
N·峰岸
奈良部晋一
渡边幸喜
柳显彦
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Abstract

本发明提供了新的下式硫代氨基甲基四唑啉酮类化合物：其中R1代表可任选地被卤素，烷氧基或烷硫基取代的烷基，可任选地被卤素取代的链烯基，可任选地被卤素取代的炔基，环烷基，任意取代的芳基，任意取代的芳烷基，可被任意取代的5-至6-员杂环，或被5-至6-员杂环取代的甲基，其中杂环可被取代，且R2和R3各独立代表如上述R1所定义的基团并可与R1相同或不同，或它们与其所键合的N原子一同形成环，所述环可进一步与烃环稠合并可在任何位置上有烷基取代基，以及上述新化合物作为除草剂的应用。

Description

具有除草活性的硫代氨基甲酰 基四唑啉酮类化合物
本发明涉及新的硫代氨基甲酰基四唑啉酮类化合物，它们的制备方法以及它们作为除草剂的应用。
人们早已知道某些四唑啉酮衍生物具有除草活性(参见日本专利特许公开昭62-12767和昭60-146879；USP.No.4956469，No.5019152和No.5003075)。
现已发现新的式(I)硫代氨基甲酰基四唑啉酮：
Figure A9611175400051
其中：
R1代表可任选地被卤素，烷氧基或烷硫基取代的烷基，可任选被卤素取代的链烯基，环烷基，可任选被卤素取代的炔基，任意取代的芳基，任意取代的芳烷基，可被任意取代的5-至6-员杂环，或被5-至6-员杂环取代的甲基，该杂环可被任意取代，上述取代基各自为至少一个选自卤素，烷基，卤代烷基，烷氧基，卤代烷氧基和烷硫基的取代基，且R2和R3各自独立代表如上述R1所定义的基团，并且可以与基团R1相同或不同，或者它们与其所键合的N-原子一同形成环，所述环可进一步与烃环稠合，并且可任意地在任何位置带有烷基作为取代基。
本发明式(I)化合物可按下述方法制得：a)在隋性溶剂存在下，并且如果合适，在酸结合剂存在下使式(II)化合物。
Figure A9611175400052
其中R1的定义同上，与式(III)化合物反应其中R2和R3的定义同上，且hal代表离去基团，如氯或溴。上述式(1)化合物显示出较强的除草活性因此可用作除草剂。
本说明书中：
术语“卤素”包括氟，氯，溴及碘，优选为氟，氯或溴，尤为氟或氯。
“烷基”可以是直链或支链的，并包括，例如，甲基，乙基，正-(或异-)丙基，正-，异-，仲-或叔-丁基，正-戊基，正-己基等，优选为C1-5烷基，尤为C1-4烷基。
“烷氧基”和烷硫基“分别是指烷基-O-基团和烷基-S-基团，其中烷基部分具有与上述“烷基”相同的合义，优选为甲氧基，乙氧基，甲硫基或乙硫基。
“链烯基”可以是直链或支链的，并包括，例如，乙烯基，烯丙基，1-丙烯基，1-，2-或3-丁烯基等，优选内C2-4烯基，优为烯丙基。
“炔基”同样也可以是直链或支链的，并且包括，例如，乙炔基，1-丙炔基，炔丙基，1-(2-或3-)丁炔基，优选为C2-4炔基，尤为炔丙基。
“环烷基”包括环丙基，环丁基，环戊基，环己基，环庚基，环辛基等，优选C3-8环烷基，尤为环丙基，环戊基，环己基，环庚基或环辛基。
“卤代烷基”是指被至少一个卤原子取代的烷基，并且包括，例如，氟甲基，二氟甲基，三氟甲基，氯甲基，溴甲基，氟乙基，二氟乙基，三氟乙基，氯乙基等。
“卤代烷氧基”是指卤代烷基-O-基团，其中卤代烷基部分的定义同上，优选为二氟甲氧基，三氟甲氧基等。
“芳基”可以是单环或多环，并且包括，例如，苯基，萘基等，优选为苯基。
“芳烷基”是指芳基取代的烷基，其中芳基部分的定义如上，并且该基团包括，例如，苄基，苯乙基等，优选为苄基。
“5-至6-员杂环”是指其中含有至少一个，优选为1或2个选自O，S和N作为环原子的杂原子的5-至6-员杂环，优选为呋喃基，噻吩基，吡唑基，噁唑基，异噁唑基，噻唑基，吡啶基，喹啉基或嘧啶基。
上述“芳基”，芳烷基“及“5-至6-员杂环”可任意地具有至少一个，优选1至3个取代基，这些取代基可以相同或不同并选自卤素，烷基，卤代烷基，烷氧基，卤代烷氧基和烷硫基。
此外，当上述式(1)中的R2和R3与它们所键合的N原子-同形成环时，所述环可以是5-至8-员环，优选5-至6-员环。除上述N原子之外，构成所述环的原子最好为碳原子，并且所述环可进一步与饱和或不饱和烃环稠合。可提及的这类环的具体实例包括：哌啶环，吡咯烷环，吲哚环，全氢吲哚环，二氢吲哚环，四氢喹啉环，全氢喹啉环等。而且，上述环可在任意位置上带有1至3个，优选1个烷基如甲基取代基。
本发明优选的一类化合物可用下述式(I)化合物举例说明，其中：
R1表示可任选地被氟，氯，溴，甲氧基，乙氧基，甲硫基或乙硫基取代的C1-5烷基，
可任选被氟或氯取代的C2-4链烯基，
可任选地被氟或氨取代的C2-4链炔基，
C3-8环烷基，
任意取代的芳基，
任意取代的芳烷基，
可被任意取代的5-至6-员杂环，或
被5-至6-员杂环取代的甲基，该杂环可被任意取代，
所述取代基各自为至少一个选自氟，氯，溴，甲基，乙基，二氟甲基，三氟甲基，甲氧基，乙氧基，二氧甲氧基，三氟甲氧基和甲硫基的基团，以及
R2和R3各自独立代表如上述R1所定义的基团，并且可以与R1相同或不同，或者它们与其所键合的氮原子一同形成哌啶，吡咯烷，吲哚、全氢吲哚，2，3-二氢吲哚或全氢喹啉，其中这些环可被甲基取代。
进一步，本发明更优选的一类的化合物的实例为其中各基团定义如上的下述式(1)化合物：
R1代表可任选的被氟，氯或溴取代的C1-4烷基，可任选地被氯取代的烯丙基，可任选地被氯取代的炔丙基，环丙基，环戊基，环己基，环庚基，环辛基，任意取代的苯基，任意取代的苄基，选自下述杂环基的5-至6-员杂环：呋喃基，噻吩基，吡唑基，噁唑基，异噁唑基，噻唑基，吡啶基，喹啉基和嘧啶基，并且它们可被任意取代，或被选自下述杂环基的5-至6-员杂环任意取代的甲基；呋喃基，噻吩基，吡唑基，噁唑基，异噁唑基，噻唑基，吡啶基，喹啉基和嘧啶基，并且所述杂环可被任意取代，
所述取代基各为至少一个选自如下的基团；氟，氯，溴，甲基，乙基，二氟甲基，三氟甲基，甲氧基，乙氧基，二氟甲氧基，三氟甲氧基和甲硫基，以及
R2和R3各自独立代表如上述R1所定义的基团，并且可以与R1相同或不同，或者它们与其所键合的N-原子一同形成哌啶，甲基取代的吡咯烷，吲哚，全氢吲哚，2，3-二氢吲哚或全氢喹啉。
当使用如1-苯基-5(4H)-四唑啉酮和N-环己基-N-乙基硫代氨基甲酰氯作为上述制备本发明化合物方法中的原料时，上述制备方法a)可用下述反应流程表示。
Figure A9611175400081
上述制备方法中，原料式(II)化合物可按类似于Journal of OrganicChemistry，vol.45，No.21(1980)，PP.5130-5136或Journal of AmericanChemical society，Vol.81(1959)，PP，3076-3079中所述的方法合成。式(II)化合物的典型实例包括下述：
1-(2-氯苯基)-5(4H)-四唑啉酮，
1-(2-氯-6-甲基苯基)-5(4H)-四唑啉酮，
1-(2，6-二氯苯基)-5(4H)-四唑啉酮，等。
上述制备方法中，原料式(III)化合物为有机化学领域公知的化合物，并且很容易通过使式(IV)化合物与硫光气反应得到
Figure A9611175400091
其中R2和R3的定义同上。
式(III)化合物的典型实例有：
N-环己基-N-乙基硫代氨基甲酰氯，
N-乙基-N-异丙基硫代氨基甲酰氯，
N-异丙基-N-苯基硫代氨基甲酰氯，
二-正-丙基硫代氨基甲酰氯，
二乙基硫代氨基甲酰基氯，
全氢吲哚-1-基-硫代氨基甲酰氯等。
上述制备方法a)通常可以使式(II)化合物与式(III)化合物反应来进行，所述反应通常是在对反应呈隋性的溶剂中进行。反应中使用的隋性有机溶剂实例包括脂族，脂环族或芳族烃类(可被任意氯化)如戊烷，己烷，环己烷，石油醚，苯，甲苯，二甲苯，氯仿，四氯化碳及1，2-二氯乙烷；醚类如乙醚，二丁醚，二噁烷，二甲氧基乙烷(DME)，四氢呋喃(THF)和二甘醇二甲醚(DGM)；腈类如乙腈；酰胺如二甲基甲酰胺(DMF)，二甲基乙酰胺(DMA)，N-甲基吡咯烷酮和1，3-二甲基-2-咪唑啉酮；砜和亚砜如二甲亚砜(DMSO)；以及碱如吡啶。
上述反应可在酸结合剂存在下进行，并且下述物质可被提及用作有用的酸结合剂的实例；无机碱，包括碱金属的碳酸盐和碳酸氢盐，如碳酸氢钠，碳酸氢钾，碳酸钠，碳酸钾等，以及有机碱，包括叔胺，二烷基氨基苯胺和吡啶类，如三乙胺，1，1，4，4-四甲基乙二胺(TMEDA)，N，N-二甲基苯胺，N，N-二乙基苯胺，吡啶，4-二甲氨基吡啶(DMAP)，1，4-二氮杂二环[2，2，2]辛烷(DABCO)及1，8-二氮杂二环[5，4，0]-十一碳-7-烯(DBU)等。
上述反应可以在较宽范围的温度下进行，但一般优选在约-50至约150℃，尤其是约0至约80℃的温度下进行。上述反应最好在常压下进行，但也可有选择地在升高或降低的压力下进行。
例如，本发明式(I)化合物可通过在1至1.5摩尔酸结合剂和4-二甲氨基吡啶存在下使1摩尔式(II)化合物与0.8至1.5摩尔式(III)化合物反应制得。
通过如结晶，色谱层析等方法可分离和纯化由此得到的式(I)化合物。
如后面的试验实施例所示，本发明的式(I)化合物具有优越的除草活性，因此它们可用作杀灭杂草的除草剂。术语“杂草”意指在不希望生长的场所所生长的所有植物。
依据所使用的浓度，本发明化合物可作为非选择性或选择性除草剂。
例如，本发明化合物可在下述杂草和作物方面用作选择性除草剂。
下列各属的双子叶杂草：欧白芥，独行菜，拉拉藤，繁缕，藜，荨麻，千里光，苋，马齿苋，苍耳，番薯，蓼，豚草，蓟，苦苣菜，茄，蔊菜，野芝麻，婆婆纳，曼陀罗，堇菜，鼬瓣花，罂粟，矢车菊，牛膝菊，节节菜，母草等。
下列各属的双子叶作物：棉花，大豆，甜菜，胡萝卜，菜豆，豌豆，茄，亚麻，番薯，野豌豆，烟草，番茄，落花生，芸苔，莴苣，香瓜，南瓜等。
下列各属的单子叶杂草：稗，狗尾草，黍，马糖，梯牧草，早熟禾，羊茅，，黑麦草，雀麦，燕麦，莎草，高梁，冰草，雨久花，飘拂草，慈姑，荸荠，藨草，雀稗，鸭嘴草，剪股颖，看麦娘，够牙根等。
下列各属的单子叶作物：稻，玉米，小麦，大麦，燕麦，黑麦，高梁，黍，风梨，天门冬，葱等。
然而，本发明化合物的用途决不受上述这些种属的限制，而且可以同样方式还扩展到其它植物。并且，依据其浓度，本发明化合物的适合于全面杀灭，例如，在工业场地和铁路路轨，以及在植有或没有植有树的小路或广场上的杂草。
同样，本发明化合物也可用于杀灭多年作物中的杂草，例如绿化林，观赏树木，果园，葡萄园，柑桔林，硬果园，香蕉种植园，咖啡种植园，茶林，橡胶种植园，油棕种植园，可可种植园，浆果种植园以及啤酒花载培地中的杂草，以及用于选择性杀灭一年生作物中的杂草。
本发明活性化物可配制成常规制剂，如溶液，乳液，可湿性粉剂，悬浮液，粉剂，可溶性粉剂，撒粉剂，片剂，乳油(suspension-emulsion concentrates)，裹在聚合物中的精细胶囊，浸渍有活性化合物的天然和合成材料等。
这些制剂可按本领域公知的方法制备，例如，混合活性化合物和增量剂(所述增量剂为液态溶剂和/或固体载体)，并任选地使用表面活性剂，即乳化剂和/或分散剂和/或发泡剂。
在使用水作为增量剂的情形下，也可以使用在有机溶剂作为辅助溶剂。至于液态溶剂，适用的主要有：芳烃，如二甲苯，甲苯或烷基萘；氯化芳烃或氯化脂族烃，如氯苯，氯化乙烯或二氯甲烷；脂族烃，如环己烷或链烷烃，例如，石油馏分，矿物油及植物油，醇，如丁醇或甘醇以及它们的醚和酯，酮，如丙酮，甲乙酮，甲基丁基酮或环己酮；强极性溶剂，如二甲基甲酰胺和二甲亚砜；以及水。
至于固态载体，适宜的有；例如，铵盐和磨碎的天然矿物质，如高岭土，粘土，滑石粉，白垩，石英，绿坡缕石，蒙脱土或硅藻土，以及磨碎的合成矿物质如高度分散的硅酸，氧化铝和硅酸盐。至于粒剂使用的固态载体，适宜的有；例如，碾碎并分级的天然岩石，如方解石，大理石，浮石，海泡石和白云石，以及合成的无机和有机粉粒，和有机材料颗粒，如锯末，椰壳，玉米芯和烟草杆。至于乳化和/或发泡剂，可适宜的有；例如非离子和阴离子乳化剂，如聚氧乙烯脂肪酸酯，聚氧乙烯脂肪醇醚，例如烷芳基聚乙二醇醚，烷基磺酸盐，烷基硫酸盐，芳基磺酸盐以及白蛋白水解产物。
至于分散剂，适宜的有：例如木质素亚硫酸盐废液和甲基纤维素。
在如粉剂，粒剂，浸渍有活性化合物的天然和合成物料或乳液的制剂中还可以任选地地使用粘合剂，可提及的这种粘合剂的实例包括：例如，羧甲基纤维素以及天然和合成聚合物，如阿拉伯树胶，聚乙烯醇和聚乙酸乙烯酯，以及天然磷脂，如脑磷脂和卵磷脂，合成磷脂。至于另外的添加剂，可使用矿物油及植物油。
有可能使用着色剂，如无机颜料，如氧化铁，二氧化钛和普鲁士兰，以及有机染料，如茜素染料，偶氮染料和金属酞菁染料，以及痕量营养剂，如金属盐，所述金属如铁，镁，硼，铜，钼和锌。
制剂中一般合有0.1至95％重量，优选0.5和90％重量的上述活性化合物。
本发明活性化合物本身或以其上述这类制剂形式，可用于杀灭杂草，并且也可与任何已知除草剂混合。混合物可以预先制成最终制剂形式，或者在使用前通过立即桶混合方式制备。
本发明活性化合物可以与植物毒性缓和剂混合，并且这种混合可以在更大程度上增宽其作为选择性除草剂的适用范围。
可例举的植物性缓和剂有1-(α，α-二甲基苄基)-3-对-甲苯基脲。
本发明活性化合物可以以其本身或上述制剂形式通过任何常规方法施用，如泼浇，喷雾，雾化(atomizing)，粉剂喷雾或粒剂播撒。
本发明活性化合物可在芽前或芽后的任何阶段施用作。同样，也可以在播种前将它们掺合到土壤内。
本发明活性化合物的施用量并不严格限制，它们可在在相当宽的范围内变化，这取决于所要求的效果，作为目标的靶植物的种类，施药的场所，施用时间等，但是，作为试验标准，活性化合物的量例如为约0.001kg/ha至约10kg/ha，优选约0.01kg/ha-约5kg/ha活性化合物。
此外，下述实验例用于说明本发明化合物的制奋和用途，但它们并不以任何方式限制本发明。其中术语“份”意指“重量份”，另有说明除外。实施例合成实施例1
将1-(苯基)-5(4H)-四唑啉酮(1.95g)和4-二甲氨基吡啶(1.59g)悬浮于乙腈(40ml)内并将此混合物室温搅拌10分钟。加入N-环己基-N-乙基硫代氨基甲酰氯(2.06g)并将混合物于50-55℃下再搅拌6小时。过滤除去盐之后，减压蒸去溶剂，残留物通过快速色谱纯化(己烷∶乙酸乙酯＝5∶2)，得到所要的1-苯基-4-(N-环己基-N-乙基硫代氨基甲酰基)-5(4H)-四唑啉酮(2.49g)。折射率n20 D＝1.5917。合成实施例2(原料的合成)
在-60℃，向硫光气(27.6g)的乙酸乙酯(400ml)溶液内滴加入N-乙基环己胺(25.45g)，三乙胺(26.3g)和乙酸乙酯(100ml)的混合物。滴加完之后，移去冰浴，室温搅拌混合物。过滤除去盐之后，减压蒸去浴剂，将如此得到的油状物质在减压下蒸馏，得到N-环己基-N-乙基硫代氨基甲酰氟(34.99g)。B.P：132-134℃/4m bar。
下述表1中示出了按与上述合成实施例1相同的方法制得的本发明式(I)化合物以及合成实施例1所制得的化合物。
表1物化常数No.   R1   R2            R3         mp.℃/n20 D1    CH3   CH3           CH32    CH3   CH3             1.56133    CH3   CH3        
Figure A9611175400143
4    CH3   C2H5        C2H5        1.55215    CH3   C2H5         C3H7-n6    CH3   C2H5        C3H7-i      1.53237    CH3   C2H5        C4H9-n8    CH3   C2H5       
Figure A9611175400144
   1.55209    CH3   C2H5       
Figure A9611175400145
10   CH3   C3H7-nC3H7-n            1.537011   CH3    C3H7-n     12   CH3   C3H7-n     
Figure A9611175400147
13   CH3   C3H7-n     
Figure A9611175400148
14   CH3   CH2CH＝CH2  CH2CH＝CH2
表1(续)No.    R1    R2           R3         mp.℃/n20 D15    CH3   CH2C≡CH     CH2C≡CH16    CH3   C3H7-i       87.5-9117    CH3
Figure A9611175400152
18    CH3
Figure A9611175400153
19    CH3
Figure A9611175400154
20    CH3
Figure A9611175400155
21    CH3
Figure A9611175400156
22    CH3 23    CH3   CH3     
Figure A9611175400158
138-139.524    CH3   CH3      25    C2H5 CH3     
表1(续)No.    R1       R2          R3       mp.℃/n20 D26    C2H5    C2H5    
Figure A9611175400161
27    C2H5    C3H7-i   28    C3H7-n  CH3       29    C3H7-n  C2H5    30    C3H7-n  C3H7-i  31    C3H7-i  CH3     
Figure A9611175400166
32    C3H7-i  C2H5    33    C3H7-i  C3H7-i  34    C4H9-n  CH3     
Figure A9611175400169
35    C4H9-n  C2H5   36    C4H9-n  C3H7-i 
Figure A96111754001611
37    C4H9-i  CH3     
Figure A96111754001612
38    C4H9-i  C2H5   
表1(续)No.    R1         R2           R3            mp.℃/n20 D39    C4H9-i     C3H7-i    
Figure A9611175400171
40    C4H9-s     CH3   
Figure A9611175400172
41    C4H9-s     C2H5      42    C4H9-s     C3H7-i   
Figure A9611175400174
43    C4H9-t     CH3       
Figure A9611175400175
44    C4H9-t     C2H5     45    C4H9-t     C3H7-i   46    C4H9-t     CH3        
Figure A9611175400178
 114.5-11747         CH3      48
Figure A96111754001711
        C2H5    
Figure A96111754001712
49
Figure A96111754001713
        C2H5       C3H7-i         1.545050
Figure A96111754001714
        C3H7-i          1.5804
表1(续)No.    R1            R2       R3           mp.℃/n20 D51         CH3    
Figure A9611175400182
52  
Figure A9611175400183
     C2H5  
Figure A9611175400184
53 
Figure A9611175400185
      C3H7-i
Figure A9611175400186
54  CH2CHCl         CH3    
Figure A9611175400187
55  CH2CHCl         C2H5   C3H7-i       1.545056  CH2CHCl         C2H5       1.546957  CH2CHCl        C3H7-i      85.5-88.558  CH2CHBr        C2H5    C3H7-i59  CH2CHBr        C2H5     60  CH2CHF         C2H5    C3H7-i61  CH2CHF         C2H5    62  CH2CF3        CH3     63  CH2CF3        C2H5    C3H7-i      1.495064  CH2CF3        C2H5   
Figure A96111754001813
   1.496965  CH2CF3        C3H7-n  C3H7-n      1.4949
表1(续)No.    R1            R2           R3              mp.℃/n20 D66  CH2CF3         C3H7-i      
Figure A9611175400191
    86.5-90.567     CH3          68
Figure A9611175400194
    C2H5      
Figure A9611175400195
69
Figure A9611175400196
    C3H7-n       C3H7-n70
Figure A9611175400197
    C3H7-i       71
Figure A9611175400199
      CH3            CH372       CH3          
Figure A96111754001911
    101.5-105.573
Figure A96111754001912
      CH3          
Figure A96111754001913
74
Figure A96111754001914
      C2H5        C2H5         1.595375
Figure A96111754001915
      C2H5        C3H7-n       1.593976       C2H5        C3G7-i       1.594977
Figure A96111754001917
      C2H5        C4H9-n       1.578378        C2H5           1.5927
表1(续)No.         R1                   R2         R3            mp.℃/n20 D79                   C2H5           1.584080                   C3H7-n    C3H7-n        1.568381  
Figure A9611175400204
                C3H7-n    
Figure A9611175400205
82                   C3H7-n    
Figure A9611175400207
83  
Figure A9611175400208
                C3H7-n     84  
Figure A96111754002010
                CH2CH＝CH2  CH2CH＝CH285  
Figure A96111754002011
                CH2C≡CH      CH2C≡CH86  
Figure A96111754002012
                C3G7-i     
Figure A96111754002013
87   88  
Figure A96111754002015
89   90  
表1(续)No.       R1                        R2            R3          mp.℃/n20 D91 92                   116.5-117.593
Figure A9611175400213
                   CH3          
Figure A9611175400214
94
Figure A9611175400215
                   CH3          
Figure A9611175400216
95                    CH3           96                    C2H5         97                C2H5        
Figure A96111754002112
     1.584898                    C3H7-n         C3H7-n      80-80.599
Figure A96111754002114
                   C3H7-n      
Figure A96111754002115
100                    C3H7-i       
表1(续)No.       R1         R2        R3           mp.℃/n20 D101    CH3      102    C2H5    103
Figure A9611175400225
   C3H7-n      C3H7-n104    C3H7-i   105
Figure A9611175400228
      CH3     
Figure A9611175400229
106
Figure A96111754002210
      C2H5     C3H7-i107       C2H5    
Figure A96111754002212
     1.5657108
Figure A96111754002213
      C3H7-n    C3H7-n        1.5670109
Figure A96111754002214
      C3H7-n  
Figure A96111754002215
110
Figure A96111754002216
      C3H7-i  
表1(续)No.   R1      R2        R3            mp.℃/n20 D111
Figure A9611175400231
CH3         1.5947112
Figure A9611175400233
CH3     113
Figure A9611175400235
C2H5    C2H5        1.5948114
Figure A9611175400236
C2H5    C3H7-n      1.5872115
Figure A9611175400237
C2H5    C3H7-i      1.5847116
Figure A9611175400238
C2H5    C4H9-n      1.5799117
Figure A9611175400239
C2H5       1.5816118 C2H5    1.5820119
Figure A96111754002313
C3H7-n    C3H7-n    1.5634120
Figure A96111754002314
C3H7-n  
Figure A96111754002315
121
Figure A96111754002316
C3H7-n     1.5778
表1(续)No.    R1                  R2              R3          mp.℃/n20 D122
Figure A9611175400241
              C3H7-n     
Figure A9611175400242
123           CH2CH＝CH2    CH2CH＝CH2124
Figure A9611175400244
              CH2C≡CH       CH2C≡CH125
Figure A9611175400245
               C3H7-i      
Figure A9611175400246
126 127
Figure A9611175400248
128 129
Figure A96111754002410
               1.6039130
Figure A96111754002411
131
Figure A96111754002412
             1.5855
表1(续)No.    R1           R2        R3          mp.℃/n20 D132    CH3       133    CH3      
Figure A9611175400254
134
Figure A9611175400255
   CH3      
Figure A9611175400256
135
Figure A9611175400257
   C2H5      C2H5          1.5954136
Figure A9611175400258
   C2H5      C3H7-i137    C2H5          1.5954138    C3H7-n    C3H7-n139
Figure A96111754002512
   C3H7-n   
Figure A96111754002513
140
Figure A96111754002514
   C3H7-i    141
Figure A96111754002516
   CH3      
表1(续)No.    R1              R2      R3          mp.℃/n20 D142   
Figure A9611175400261
  C2H5      C3H7-i143      C2H5    
Figure A9611175400263
    1.5446144      C3H7-n    C3H7-n145      C3H7-n   146   
Figure A9611175400267
  C3H7-i   147   
Figure A9611175400269
  C2H5    C3H7-i148   
Figure A96111754002610
  C2H5       1.4746149   
Figure A96111754002612
  C3H7-n    C3H7-n    80.5-83150   
Figure A96111754002613
  C3H7-n  
Figure A96111754002614
151   
Figure A96111754002615
  C3H7-i   152      C2H5      C3H7-i
表1(续)No.    R1               R2         R3             mp.℃/n20 D153     C2H5    
Figure A9611175400272
       1.5375154  
Figure A9611175400273
  C3H7-n    C3H7-n155  
Figure A9611175400274
  C3H7-n  
Figure A9611175400275
156     C3H7-i   157  
Figure A9611175400278
  CH3     
Figure A9611175400279
158  
Figure A96111754002710
  C2H5    C2H5              98-103.5159  
Figure A96111754002711
  C2H5   160  
Figure A96111754002713
  C3H7-n  C3H7-n161  
Figure A96111754002714
  C3H7-i   162  
Figure A96111754002716
  CH3    
Figure A96111754002717
163     C2H5  
Figure A96111754002719
表1(续)No.    R1             R2          R3          mp.℃/n20 D164     C3H7-n    C3H7-n165  
Figure A9611175400282
  C3H7-i     
Figure A9611175400283
166     CH3        167  
Figure A9611175400286
  C2H5      168     C3H7-n    C3H7-n169  
Figure A9611175400289
  C3H7-i     
Figure A96111754002810
170     CH3        171     C2H5      
Figure A96111754002814
172  
Figure A96111754002815
  C3H7-n     C3H7-n173     C3H7-i     174  
Figure A96111754002818
  CH3      
Figure A96111754002819
表1(续)No.    R1               R2        R3                 mp.℃/n20 D175   C2H5   
Figure A9611175400292
176   C3H7-n  C3H7-n177  
Figure A9611175400294
C3H7-i   178      CH3       179  
Figure A9611175400298
   C2H5     180  
Figure A96111754002910
   C3H7-n  C3H7-n181      C3H7-i   182   
Figure A96111754002913
   CH3   
Figure A96111754002914
183  
Figure A96111754002915
   C2H5  
Figure A96111754002916
184  
Figure A96111754002917
   C3H7-n    C3H7-n185  
Figure A96111754002918
   C3H7-i  
Figure A96111754002919
186  
Figure A96111754002920
   CH3     
表1(续)No.    R1              R2        R3               mp.℃/n20 D187  
Figure A9611175400301
  C2H5     188     C3H7-n    C3H7-n189  
Figure A9611175400304
  C3H7-i  
Figure A9611175400305
190  
Figure A9611175400306
  CH3      191     C2H5    192  
Figure A96111754003010
  C3H7-n    C3H7-n193     C3H7-i   194  
Figure A96111754003013
  CH3    
Figure A96111754003014
195  
Figure A96111754003015
  C2H5   
Figure A96111754003016
196  
Figure A96111754003017
  C3H7-n    C3H7-n197     C3H7-i  
Figure A96111754003019
198  
Figure A96111754003020
  CH3      
Figure A96111754003021
表1(续)No.    R1               R2          R3              mp.℃/n20 D199  
Figure A9611175400311
  C2H5    
Figure A9611175400312
200     C3H7-n    C3H7-n201     C3H7-i   202  
Figure A9611175400316
  CH3     
Figure A9611175400317
203  
Figure A9611175400318
  C2H5   
Figure A9611175400319
204  
Figure A96111754003110
  C3H7-n    C3H7-n205  
Figure A96111754003111
  C3H7-i  
Figure A96111754003112
206     CH3      207     C2H5   
Figure A96111754003116
208     C3H7-n    C3H7-n209     C3H7-i  
Figure A96111754003119
210  
Figure A96111754003120
  CH3     
表1(续)No.       R1                   R2         R3          mp.℃/n20 D211     C2H5   
Figure A9611175400322
212        C3H7-n   C3H7-n213  
Figure A9611175400324
     C3H7-i  
Figure A9611175400325
214  
Figure A9611175400326
     CH3        215        C2H5    
Figure A9611175400329
216        C3H7-n    C3H7-n217        C3H7-i   218       CH3     
Figure A96111754003214
219  
Figure A96111754003215
    C2H5  
Figure A96111754003216
220       C3H7-n    C3H7-n221  
Figure A96111754003218
    C3H7-i   
Figure A96111754003219
222  
Figure A96111754003220
      CH3       223  
Figure A96111754003222
       C2H5      224          C3H7-n      C3H7-n
表1(续)No.    R1                R2          R3        mp.℃/n20 D225  
Figure A9611175400331
    C3H7-i  
Figure A9611175400332
226      CH3       227  
Figure A9611175400335
   C2H5    228      C3H7-n    C3H7-n229  
Figure A9611175400338
   C3H7-i   230  
Figure A96111754003310
   CH3     
Figure A96111754003311
231  
Figure A96111754003312
  C2H5   
Figure A96111754003313
232      C3H7-n    C3H7-n233  
Figure A96111754003315
   C3H7-i   234  
Figure A96111754003317
   CH3     235      C2H5   
Figure A96111754003320
236      C3H7-n    C3H7-n237  
Figure A96111754003322
   C3H7-i  
Figure A96111754003323
238  
Figure A96111754003324
  CH3     239  
Figure A96111754003326
  C2H5   
Figure A96111754003327
No.          R1               R2           R3         mp.℃/n20 D240    
Figure A9611175400341
    C3H7-n    C3H7-n241    
Figure A9611175400342
    C3H7-i   
Figure A9611175400343
242    
Figure A9611175400344
    CH3        243    
Figure A9611175400346
    C2H5     
Figure A9611175400347
244    
Figure A9611175400348
    C3H7-n    C3H7-n245    
Figure A9611175400349
    C3H7-i   
Figure A96111754003410
246    
Figure A96111754003411
    CH3   
Figure A96111754003412
247         C2H5    
Figure A96111754003414
248         C3H7-n    C3H7-n249    
Figure A96111754003416
    C3H7-i   
Figure A96111754003417
250         CH3      
Figure A96111754003419
251    
Figure A96111754003420
    C2H5     252    
Figure A96111754003422
    C3H7-n    C3H7-n253    
Figure A96111754003423
    C3H7-i    254    
Figure A96111754003425
    CH3      
Figure A96111754003426
表1(续)No.        R1                    R2           R3        mp.℃/n20 D255        C2H5     
Figure A9611175400352
256          C3H7-n    C3H7-n257          C3H7-i   
Figure A9611175400355
258               CH3        CH3259                  CH3              1.5869260    
Figure A9611175400359
             CH3       261                  C2H5    C2H5262    
Figure A96111754003512
            C2H5    C3H7-n263                 C2H5    C3H7-i           1.5695
表1(续)No.         R1          R2             R3      mp.℃/n20 D264    
Figure A9611175400361
   C2H5       C4H9-n265        C2H5      
Figure A9611175400363
      1.5791266    
Figure A9611175400364
   C2H5             1.5783267        C3H7-n      C3H7-n        92-95268    
Figure A9611175400367
   C3H7-n      269    
Figure A9611175400369
   C3H7-n     
Figure A96111754003610
      1.5785270        C3H7-n       271       CH2CH＝CH2    CH2CH＝CH2
表1(续)No.          R1                 R2            R3        mp.℃/n20 D272               CH2C≡CH    CH2C≡CH273   
Figure A9611175400372
             C3H7-i   274   
Figure A9611175400374
275
Figure A9611175400375
276 277 278 279
Figure A9611175400379
表1(续)No.       R1           R2         R3          mp.℃/n20 D280    
Figure A9611175400381
   CH3     
Figure A9611175400382
281    
Figure A9611175400383
   CH3     
Figure A9611175400384
282    
Figure A9611175400385
 CH3     
Figure A9611175400386
283    
Figure A9611175400387
   C2H5     284         C3H7-n     C3H7-n       82-85285    
Figure A96111754003810
    C3H7-i   
Figure A96111754003811
286    
Figure A96111754003812
   CH3       287    
Figure A96111754003814
    C2H5   
Figure A96111754003815
表1(续)No.          R1           R2          R3         mp.℃/n20 D288    C3H7-n    C3H7-n289   
Figure A9611175400392
     C3H7-i     290   
Figure A9611175400394
    CH3        
Figure A9611175400395
291         C2H5       
Figure A9611175400397
292   
Figure A9611175400398
     C3H7-n      C3H7-n      72.5-79293          C3H7-i     
Figure A96111754003910
294      CH3          CH3         99-100.5295   
Figure A96111754003912
  CH3         296      C2H5        C2H5      1.5655
表1(续)No.       R1               R2           R3           mp.℃/n20 D297   
Figure A9611175400401
   C2H5    
Figure A9611175400402
298   
Figure A9611175400403
   C3H7-n    C3H7-n299   
Figure A9611175400404
   C3H7-i   
Figure A9611175400405
300       CH3        CH3           110-120301       CH3      
Figure A9611175400408
302       C2H5     
Figure A96111754004010
303       C3H7-n    C3H7-n304       C3H7-i   
Figure A96111754004013
305   
Figure A96111754004014
    CH3        CH3           85-90306   
Figure A96111754004015
    CH3       
Figure A96111754004016
307   
Figure A96111754004017
   C2H5     
Figure A96111754004018
308   
Figure A96111754004019
    C3H7-n     C3H7-n
表1(续)No.       R1              R2           R3      mp.℃/n20 D309    C3H7-i   
Figure A9611175400412
310       CH3       
Figure A9611175400414
311   
Figure A9611175400415
   C2H5     C2H5       1.5846312   
Figure A9611175400416
   C2H5     C3H7-i     1.5821313   
Figure A9611175400417
   C2H5     314       C3H7-n     C3H7-n315   
Figure A96111754004110
   C3H7-i   
Figure A96111754004111
316       CH3     
表1(续)No.        R1               R2            R3           mp.℃/n20 D317   
Figure A9611175400421
   C2H5     
Figure A9611175400422
318   
Figure A9611175400423
   C3H7-n      C3H7-n319       C3H7-i     320   
Figure A9611175400426
   CH3         
Figure A9611175400427
321   
Figure A9611175400428
   C2H5       C2H5           1.6039322   
Figure A9611175400429
   C2H5        323       C3H7-n      C3H7-n324   
Figure A96111754004212
   C3H7-i       
Figure A96111754004213
325   
Figure A96111754004214
     C2H5          C3H7-i
表1(续)No.           R1          R2         R3             mp.℃/n20 D326   
Figure A9611175400431
   C2H5    
Figure A9611175400432
327       C3H7-n    C3H7-n328   
Figure A9611175400434
   C3H7-i    329          C2H5      C3H7-i330          C2H5     
Figure A9611175400438
331   
Figure A9611175400439
      C3H7-n    C3H7-n332   
Figure A96111754004310
      C3H7-i    333   
Figure A96111754004312
   C2H5      C3H7-i          1.5854334       C2H5    
Figure A96111754004314
        1.5878335   
Figure A96111754004315
   C3H7-n    C3H7-n336   
Figure A96111754004316
   C3H7-i   
Figure A96111754004317
表1(续)No.        R1                 R2            R3             mp.℃/n20 D337       C2H5      C3H7-i338   
Figure A9611175400442
   C2H5      339   
Figure A9611175400444
   C3H7-n      C3H7-n340   
Figure A9611175400445
   C3H7-i      341       C2H5        C3H7-i342   
Figure A9611175400448
   C2H5       343       C3H7-n        C3H7-n
表1(续)No.         R1              R2            R3            mp.℃/n20 D344   
Figure A9611175400451
   C3H7-i    345   
Figure A9611175400453
   C2H5       C3H7-i         1.5530346       C2H5     
Figure A9611175400455
        1.5634347       C3H7-n    C3H7-n348       C3H7-i   
Figure A9611175400458
349       C2H5      C3H7-i350       C2H5     
表1(续)No.          R1             R2          R3          mp.℃/n20 D351   
Figure A9611175400461
   C3H7-n     C3H7-n352   
Figure A9611175400462
   C3H7-i     353   
Figure A9611175400464
   C2H5     C3H7-i354       C2H5     355   
Figure A9611175400467
   C3H7-n     C3H7-n356       C3H7-i    
Figure A9611175400469
357   
Figure A96111754004610
    C2H5       C3H7-i
表1(续)No.           R1            R2         R3          mp.℃/n20 D358   
Figure A9611175400471
   C2H5    359   
Figure A9611175400473
   C3H7-n    C3H7-n360       C3H7-i   
Figure A9611175400475
361   
Figure A9611175400476
         C2H5      C3H7-i362             C2H5     
Figure A9611175400478
363             C3H7-n      C3H7-n364             C3H7-i      365   
Figure A96111754004712
     C2H5        C3H7-i      1.5488
表1(续)No.          R1           R2          R3         mp.℃/n20 D366       C2H5   
Figure A9611175400482
     1.5563367   
Figure A9611175400483
   C3H7-n    C3H7-n368   
Figure A9611175400484
   C3H7-i    369       C2H5      C3H7-i370       C2H5   
Figure A9611175400488
371       C3H7-n    C3H7-n372   
Figure A96111754004810
   C3H7-i   
Figure A96111754004811
373   
Figure A96111754004812
        C2H5      C3H7-i
表1(续)No.        R1                 R2           R3         mp.℃/n20 D374   
Figure A9611175400491
          C2H5    375   
Figure A9611175400493
          C3H7-n    C3H7-n376   
Figure A9611175400494
          C3H7-i    377   
Figure A9611175400496
   C2H5    C3H7-i378   
Figure A9611175400497
   C2H5    379       C3H7-n    C3H7-n380   
Figure A96111754004910
   C3H7-i   
Figure A96111754004911
381              C2H5    C3H7-i382   
Figure A96111754004913
          C2H5   
Figure A96111754004914
383   
Figure A96111754004915
          C3H7-n    C3H7-n
表1(续)No.           R1         R2           R3      mp.℃/n20 D384       C3H7-i   
Figure A9611175400502
385   
Figure A9611175400503
   C2H5      C3H7-i386       C2H5     
Figure A9611175400505
387       C3H7-n     C3H7-n388       C3H7-i    
Figure A9611175400508
389       C2H5       C3H7-i390       C2H5        1.5840391   
Figure A96111754005012
   C3H7-n     C3H7-n392       C3H7-i    
Figure A96111754005014
393   
Figure A96111754005015
   C2H5       C3H7-i      1.5831
表1(续)No.          R1            R2          R3          mp.℃/n20 D394   
Figure A9611175400511
       C2H5           1.5860395           C3H7-n    C3H7-n396         C3H7-i   397       C2H5    C3H7-i398   
Figure A9611175400517
   C2H5    
Figure A9611175400518
399       C3H7-n    C3H7-n400   
Figure A96111754005110
   C3H7-i   
Figure A96111754005111
401   
Figure A96111754005112
   C2H5     C3H7-i402       C2H5   
Figure A96111754005114
表1(续)No.        R1                   R2              R3       mp.℃/n20 D403   
Figure A9611175400521
            C3H7-n         C3H7-n404   
Figure A9611175400522
            C3H7-i         
Figure A9611175400523
405    CH3                           
Figure A9611175400524
406    CH2CF3                         
Figure A9611175400525
407    CH2CF3                         
Figure A9611175400526
408   
Figure A9611175400527
409    410    试验实施例1
对耕地杂草的芽前土壤处理试验制备方法载体：丙酮5份乳化剂；苄氧基聚乙二醇醚1份
将1份活性化合物和上述量的载体和乳化剂混合制得乳液。将规定量的这种乳液用水稀释以进行下述试验。试验方法
在温室中，将碑和野苋种子各自播种到装在120cm2盆内的耕地土的表层内，用土覆盖，向试验盆的土壤表层上均匀喷洒规定量上述试验农药。播种4周后，检查除草效果。在完全杀死情形下，除草效果评定为100％，在与未处理情形相比，观察到同样生长情况下，除草效果评定为0％。结果
在1kg/ha有效成分施药量下，16号，50号，57号和80号化合物对碑和野苋显示出100％的除草效果。试验实施例2
稻田杂草除草效果试验试验方法
在温室中，将2.5叶期(15cm高)的水稻秧苗(品种：Nipponbare)按每堆3株标准移载到盛有稻田土且面积为1/2000公亩的大盆(25×20×9cm)的两处地方。然后，播种稗，异型莎草(Smallflower)，鸭舌草，阔叶杂草[母草(commonfalsepimpernel)，印度分枝节节菜，三蕊沟繁缕，水苋菜(Ammannia multiffora Roxb)，虻眼(Dopatrium junceum Hammilt)等]以及灯心草的种子，并给盆浇水至水深约高出土壤表面2-3cm。水稻秧苗移栽5天后，将按上述制备步骤所制得的试验农药施加到水面上。处理后三周，检查除草效果和对作物的药害程度，在此其间保持盆中水深3cm。
在完全死亡情形下，除草效果评定为100％，在未观察到除草效果的情形下，除草效果评定为0％。结果
在1kg/ha有效成分施药量情形下，16号，50号，57号，66号，74号，80号，113号，115号，346号及365号化合物显示出90％或更高的除草效果。制剂实施例1(粒剂)
将25份水加到含10份16号化合物，30份膨润土(蒙脱土)，58份滑石和2分木素磺酸盐的混合物中，充分混合，随后采用挤压成粒机成粒成10-40目颗粒，于40-50℃干燥，得到粒剂。制剂实施例2(粒剂)
在旋转下，向装有95份0.2-2mm粒度分布的粘土矿颗粒和5份50号化合物的旋转混合器内喷洒液态稀释剂进行均匀湿润，随后于40-50℃干燥，得到粒剂。制剂实施例3(乳液)
通过搅拌混合30份66号化合物，55份二甲苯，8份聚氧乙烯烷基苯基醚和7份烷基苯磺酸钙可制得乳液。制剂实施例4(可湿性粉剂)
可湿性粉剂按下述方法制备：碾碎并混合15份113号化合物，80份白碳(不定形水合二氧化硅细粉)和粉状粘土的混合物(1∶5)，2份烷基苯磺酸钠和3份烷基萘磺酸钠和甲醛的缩合物。制剂实施例5(可湿性粒剂)
按下述方法制备可湿性粒剂：充分混合20份57号化合物，30份木素磺酸钠，15份煅烧膨润土和35份煅烧硅藻土粉，然后加水并通过0.3mm筛挤压所形成的混合物，随后干燥。

Claims (8)

1.新的式(I)硫代氨基甲酰基四唑啉酮化合物其中
R1代表可任选地被卤素，烷氧基或烷硫基取代的烷基，可任选地被卤素取代的的链烯基，环烷基，可任选地被卤素取代的炔基，任意取代的芳基，任意取代的芳烷基，可被任意取代的5-至6-员杂环，或被5-至6-员可被任意取代的杂环取代的甲基，上述取代基各自为至少一个选自卤素，烷基，卤代烷基，烷氧基，卤代烷氧基和烷硫基的基团，以及
R2和R3各自独立代表如上述R1所定义的基团，并可以与R1相同或不同，或者它们其所键合N-原子-同形成环，所述环可进一步与烃环稠合，并且可任意地在任何位置带有烷基作为取代基。
2.根据权利要求1的化合物，其中
R1代表可任选地被下述基团取代的C1-5烷基：氟，氯，溴，甲氧基，乙氧基，甲硫基或乙硫基，
可任选地被氟或氯取代的C2-4链烯基，
可任选地被氟或氯取代的C2-4炔基，
C3-8环烷基，
任意取代的芳基，
任意取代的芳烷基，
可被任意取代的5-至6-员杂环，或
被5-至员6-员可被任意取代的甲基，
上述取代基各自为至少一个选自下述的基团：氟，氯，溴，甲基，乙基，二氟甲基，三氟甲基，甲氧基，乙氧基，二氟甲氧基，三氟甲氧基和甲硫基，以及
R2和R3各自独立代表如上述R1所定义的基团，并且可以与R1相同或不同，或者它们与其所键合的氮原子一同形成哌啶，吡咯烷，吲哚，全氢吲哚，2，3-二氢吲哚或全氢喹啉，这些环可被甲基取代。
3.根据权利要求1的化合物，其中
R1代表可任选地被氟，氯或溴取代的C1-4烷基，可任选地被氯取代的烯丙基，可任选地被氯取代的炔丙基，环丙基，环戊基，环己基，环庚基，环辛基，任意取代的苯基，任意取代的苄基，选自下述杂环基的5-至6-员杂环：呋喃基，噻吩基，吡唑基，噁唑基，异噁唑基，噻唑基，吡啶基，喹啉基和嘧啶基，并且这些杂环可任意被取代，或被选自下列杂环基的5-至6-员杂环取代的甲基：呋喃基，噻吩基，吡唑基，噁唑基，异噁唑基，噻唑基，吡啶基，喹啉基和嘧啶基，并且这些杂环基可任意被取代，
上述取代基各自为至少一个选自下述的基团：氟，氯，溴，甲基，乙基，二氟甲基，三氟甲基，甲氧基，乙氧基，二氟甲氧基，三氟甲氧基和甲硫基，以及
R2和R3各自独立代表如上述R1所定义的基团，并且可以与R1相同或不同，或者它们与其所键合的氮原子一同形成哌啶，甲基取代吡咯烷，吲哚，全氢吲哚，2，3-二氢吲哚或全氢喹啉。
4.制备式(I)化合物方法：
Figure A9611175400031
其中
R1代表可任选地被卤素，烷氧基或烷硫基取代的烷基，
可任选地被卤素取代的链烯基，
环烷基，
可任选地被卤素取代的炔基，
任意取代的芳基，
任意取代的芳烷基，
可被任意取代的5-至6-员杂环，或
被5-至6-员可被任意取代的杂环取代的甲基，
上述取代或各自为至少一个选自下述的基团；卤素，烷基，卤代烷基，烷氧基，卤代烷氧基和烷硫基，以及
R2和R3各自独立代表如上述R1所定义的基团，并且可以与R1相同或不同，或者它们与其所键合的氮原子一同形成环，所述环可进一步与烃环稠合，并且可任意地在任何位置带有烷基作为取代基，其特征是在隋性溶剂存在下，并且如果合适，在酸结合剂存在下使式(II)化合物
其中R1的定义同上，与式(III)化合物反应：
Figure A9611175400042
其中R2和R3的定义同上，且hal代表离去基团，如氯或溴。
5.除草组合物，其特征是它们含有至少一种式(I)硫代氨基甲酰基四唑啉酮。
6.杀灭杂草的方法，其特征是使式(I)硫代氨基甲酰基四唑啉酮作用于杂草和/或它们的生长环境。
7.式(I)硫代氨基甲酰基四唑啉酮在杀灭杂草方面的应用。
8.制备除草组合物的方法，其特征是使式(I)硫代氨基甲酰基四唑啉酮与增量剂和/或表面活性剂混合。
CN96111754A 1995-08-02 1996-08-02 具有除草活性的硫代氨基甲酰基四唑啉酮类化合物 Expired - Fee Related CN1064679C (zh)

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