CN1024985C - 一种新的三唑杀虫组合物及其应用 - Google Patents
一种新的三唑杀虫组合物及其应用 Download PDFInfo
- Publication number
- CN1024985C CN1024985C CN89102293A CN89102293A CN1024985C CN 1024985 C CN1024985 C CN 1024985C CN 89102293 A CN89102293 A CN 89102293A CN 89102293 A CN89102293 A CN 89102293A CN 1024985 C CN1024985 C CN 1024985C
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- CN
- China
- Prior art keywords
- tert
- triazole
- butyl group
- base
- dimethylamino formoxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 81
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 125000005879 dioxolanyl group Chemical group 0.000 claims description 7
- 125000002541 furyl group Chemical group 0.000 claims description 7
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
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- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229940124530 sulfonamide Drugs 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- RAPZOMPOJASZJS-UHFFFAOYSA-N tetracyclo[6.4.0.02,4.05,7]dodec-1(12)-ene Chemical compound C12=CCCCC2C2CC2C2C1C2 RAPZOMPOJASZJS-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003777 thiepinyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003583 thiosemicarbazides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 125000004306 triazinyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- GCRCSLNXFKCFHB-UHFFFAOYSA-N triethyl(hexyl)azanium Chemical compound CCCCCC[N+](CC)(CC)CC GCRCSLNXFKCFHB-UHFFFAOYSA-N 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本发明涉及下式1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑,其中取代基如说明书所述,还涉及含此化合物的组合物和应用方法。
Description
本发明涉及可用作杀虫剂的新1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑、含该化合物的组合物和应用方法。
已提出某些具有杀虫活性的1,2,4-三唑。
US3308131说明了下式的一组1,2,4-三唑:
其中X为O或S,R1和R2为高达14碳的脂肪基,并可与氨基甲酰基的氮原子连成杂环,R3和R4一起含高达14碳,其中无脂族不饱和键,可选自H,卤素,磺酰基,巯基,氰基,烃基,卤代烃基,硝基烃基,羟基(二价)碳氧羰基烃基(hydroxycarbyloxycarbonylhydrocarbyl),烃基磺酰基,烃基巯基,硝基烃基巯基,卤代烃基巯基,氨基烃基巯基和烃氧烃基。据公开,这些化合物可用作杀虫剂,纺织纤维染色剂和止痛药。
US4,291,043公开了具有杀虫活性的1-N,N-二甲胺基甲酰基-3(5)-烷基-5(3)烷基硫基烷基硫基-1,2,4-三唑。3(5)位取代包括异丙基,仲丁基,叔丁基或根据需要选择甲基取代的环丙基和下式基团:
-S-CH(R′)-(CH2)n-S-R″
其中R′为H或甲基,R″为1-4碳烷基,n为0或1。
US3973028和4038387公开了具有杀虫活性的1-二甲胺基甲酰基-3-支化烷基-1,2,4-三唑-5-基-(N-取代)磺酰胺。支化烷基包括3-4碳仲或叔烷基和环烷基。
US4054664公开了具有杀虫活性的1(2)-(N,N-二取代氨基甲酰基)-3,5-取代-1,2,4-三唑。3(5)位取代基包括异丙基,仲丁基,叔丁基和-SR,其中R为甲基,乙基,丙基,乙烯基,2-丙炔基,2-丁烯基或2-卤代烷基。
US4255435公开了对多种经济上重要的昆虫和线虫具有驱杀活性的1(2)-N。N-二取代氨基甲酰基-3,5-取代-1,2,4-三唑。3(5)位取代基包括异丙基,仲丁基,叔丁基。5(3)位取代基包括SR,其中R为甲基,乙基,丙基,乙烯基,2-丙炔基,2-丁烯基和2-卤代烷基。
US4160839公开了具有杀虫活性的1-N,N-二甲胺基甲酰基-3,5-取代-1,2,4-三唑。3位取代基包括叔丁基,丙基,环丙基,异丙基或1-甲基丙基。5位取代基包括SR,其中R为2-丙炔基,烯丙基,2-溴烯丙基,2-氯烯丙基,2-甲基烯丙基,1-甲基烯丙基或2,3,3-三氯烯丙基。
US4220790和4066774公开了具有杀虫活性的1-N,N-二甲胺基甲酰基-3-叔丁基-5-甲基硫基-1,2,4-三唑和用该三唑杀虫的方法。
DE3031191A1公开了具有杀虫活性的1-二甲胺基甲酰基-3-(或5)-苄基硫基-5-(或3)-烷基-1,2,4-三唑。5(或3)位取代基包括异
丙基,仲丁基,叔丁基,或根据需要选择甲基取代的环丙基。
DE3021232公开了具有杀虫活性的1-二甲胺基甲酰基-1,2,4-三唑。3(或5)位由下式基团取代:
其中R′为1-4碳烷基,R2为H或甲基,n为0或1。
EP0029407公开了具有杀虫活性的1-N,N′-二甲胺基甲酰基-3,5-取代-1,2,4-三唑。3位取代基包括异丙基,仲丁基,叔丁基或环丙基。5位取代基包括S(CH2)nOR2,其中R2为1-3碳烷基,n为1或2。
本发明涉及1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑。这些化合物的主要区别在其5位新取代基。
本发明化合物的区别还在其对同翅目,特别是蚜科等内吸性昆虫的杀虫活性。因此,本发明化合物特别适于控制栽培作物和观赏植物园,特别是水果和蔬菜园中咬食植物的昆虫。
因此本发明目的是提出具有杀虫活性的新化合物及含该化合物的组合物。本发明另一目的是提出用此新化合物控制昆虫的方法。
本发明提出下式化合物
其中:W是叔丁基、仲丁基、异丙基、环丙基、1-甲硫基-1-甲基乙基或1-甲基环丙基-1-基;
R′是未取代的或取代的-(CH2)n-,该取代的基团上有从以下基团中独立地选出的一至四个相同或不同取代基;氰基、硝基、卤素、-OR、-CO2R、-OCOR、-COR、(C2-C6)链烯基、(C2-C6)炔基、(C1-C6)烷基、(C1-C6)卤代烷基;未取代的或取代的苯基,其中取代的苯基上有从以下基团中独立地选出的一至三个相同或不相同取代基:卤素、氰基、硝基、三氟甲氧基、二氟甲氧基、四氟乙氧基、三氟甲硫基、四氟乙硫基、-CO2R、-COR、-OCOR、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)卤代烷基或(C2-C6)链烯基,X是未取代的(C1-C4)二烷氧烷基,它的每个烷基基团独立地具有所述的碳原子数:取代的(C1-C4)二烷氧烷基,该基团的每个烷基独立地具有所述的碳原子数,该基团有一至三个取代基;未取代的(5-14)员杂环;或具有一至三个取代基取代的(5-14)员杂环;杂环上具有独立地从氧、氮、硫中选出的一至三个相同或不同的杂原子;在二烷氧烷基或杂环上的取代基是独立地从以下基团中选用的:卤素、氰基、硝基、氨基、-NRCOR2、-COOR、-CONRR2、-COR、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)烷硫基、(C1-C4)卤代烷基、(C1-C4)卤代烷氧基、(C1-C4)多卤代烷基和(C1-C4)多卤代烷氧基;此处R和R2可是相同的或不同的,它们表示氢、未取代的或有一至三个取代基取代的(C1-C6)烷基、未取代的或有一至三个取代基取代的苯基;其中所说的取代基是独立地从以下基团中选用的:卤素、氰基、硝基、羟基、三氟甲氧基、二氟甲氧基、四氟乙氧基、三氟甲硫基、四氟乙硫基、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)卤代烷基、(C2-C6)链烯基、羧基、(C1-C4)烷氧羰基;
n是1-6的一个整数;
还涉及它们的适于农用的盐类。
此外,本发明还提供了含有本发明化合物的组合物,以及所说化合物及组合物的使用方法。
“卤素”一词包括了氟、氯、溴、碘。“烷基”包括了直链或支链基团,如甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、新戊基、异辛基及其类似物。“杂环”应理解为包括芳环类,如吖啶基、氮杂卓基、苯并咪唑基、苯并异噁唑基、2,3-苯并二嗪基、苯并呋喃基、苯并吡喃基、苯并吡喃酮基、苯并噻唑基、苯并硫代呋喃基、苯并噁唑基、苯并吡唑基、咔唑基、二氧吲基(dioxinyl)、呋喃基、咪唑基、吲哚基、异吲哚基(isobenzazolyl)、异苯并呋喃基、异苯并吡喃基、异苯并硫代基、异氮(杂)茚基、异喹啉基、异噁唑基、naphthriyidinyl、噁二唑基、噁嗪基、噁唑基、oxepinyl、苯二(甲)酰亚氨基(phthalimidolyl)、吡喃基、吡嗪基、吡唑基、哒嗪基、吡啶基、嘧啶并基(pyrimidoyl)、4-氮茚
基、吡咯酮基、吡咯甲酰、喹唑啉基、喹啉基、噻唑基、噻吩基、噻坪基(thiepinyl)、噻吨基(thioxanthyl)、三嗪基、三唑基、呫吨基及其类似物。“杂环”也指部分地和全部地包括了以上提到的饱和的杂环衍生物,这些包括(但不限于)吡咯烷基、哌啶、吗啉基、二氧戊环基、二噁烷基、四氢吡喃基、噻唑啉基、噁唑烷酮基(oxazolidinonyl)、异噁唑啉基和类似物。
优先选用的是满足以下几点的本发明化合物,在式Ⅰ中,W是叔丁基;
R′是未取代的-(CH2)n-或具有一至四个相同的或不同的取代基的-(CH2)n-,其中的取代基是从以下基团中独立地选出的:(C1-C6)烷基、(C1-C6)卤代烷基、卤素、硝基和氰基;
X是未取代的(C1-C8)二烷氧烷基或有一至三个取代基的(C1-C8)二烷氧烷基;从以下基团中选出的未取代的或取代的杂环;三唑基、吡啶基、二噁烷基、二氧戊环基、四氢吡喃基、噁唑烷酮基、异噁烷基、呋喃基、吡嗪基、苯二(甲)酰亚氨基、喹啉基;还可以是有一至三个取代基的杂环,其上的取代基独立地选自于(C1-C4)烷基和(C1-C4)卤代烷基;
n是1-6的一个整数。
更为优先选用的是满足以下几点的式Ⅰ表示的化合物:
W是叔丁基;
R′是-CH2-或-CH(CH3)-,和
X是未取代的或被(C1-C4)烷基取代的(C1-C8)二烷氧烷基、三唑基、吡啶基、二氧戊环基、二噁烷基、四氢吡喃基、噁唑烷酮基、异噁唑基、呋喃基、吡嗪基、苯二(甲)酰亚氨基或喹啉基
最优选的是满足下面几点的式Ⅰ表示的化合物:
W是叔丁基;
R′是-CH2-
X是二噁烷基、二氧戊环基、呋喃基或三唑基,
因为式Ⅰ表示的1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑可能具有酸性或碱性官能团,它们能够与恰当的碱或酸形成新的盐类,其盐类也具有杀虫活性。
典型的盐是农学上可接受的金属盐、铵盐和酸加成盐。金属盐中的阳离子有碱金属阳离子如钠、钾、锂或类似物;有碱土金属阳离子如钙、镁、钡、锶或类似物;还有重金属阳离子如锌、镁、二价铜、一价铜、三价铁、二价铁、钛、铝或类似物。铵盐中的铵阳离子用式NR9R10R11R12表示,其中,R9、R10、R11、R12中的任一个独立地代表一个氢原子、一个羟基、一个(C1-C4)烷氧基、一个(C1-C20)烷基、一个(C3-C8)链烯基、一个(C3-C8)炔基、一个(C2-C8)羟烷基、一个(C2-C8)烷氧烷基、一个(C2-C6)氨烷基、一个(C2-C6)卤代烷基、一个氨基、一个(C1-C4)烷基或(C1-C4)二烷基胺基、一个未取代的或取代的苯基、一个取代的或未取代的苯基烷基,其烷基部分可含多至四个碳原子,或者R9、R10、R11、R12中的任意两个可与铵上氮原子一起形成一个(5-6)员杂环,需要时环上还可有另一个杂原子(如氧、氮或硫),倾向于选用饱和的杂环如哌啶子基、吗啉代基、吡咯烷基(pyrrolidino)、哌嗪基(piperazino)或类似物,或者R9、R10、R11、R12中任意三个与铵上氮原子一起可形成一个(5-6)员芳香族杂环,如哌唑(piperazole)或吡啶。若铵上含有一个取代的苯基或取代的苯基烷基,则取代基通常选自于以下基团:卤素、(C1-C8)烷基、(C1-C4)烷氧基、羟基、硝基、三氟甲基、氰基、氨基、(C1-C4)烷硫基及其类似物。这种取代的苯基最好具有多至二个的取代基。典型的铵阳离子包括铵、二甲基铵、2-乙基己基铵、双(2-羟乙基)铵、三(2-羟乙基)铵、二环己基铵、叔辛基铵、2羟乙基铵、吗啉鎓(morpholinium)、哌啶鎓(piperidinium)、2-苯乙基铵、2-甲基苄铵、正己铵、三乙铵、三甲铵、三(正丁基)铵、甲氧乙基铵、二异丙基铵、吡啶鎓二烷基铵、二氢化吡唑鎓、炔丙基铵、二烷基
、十八烷基铵、4-氯代苯基铵、4-硝基苄基铵、苄基三甲基铵、2-羟乙基二甲基十八烷基铵、2-羟乙基二乙基辛基铵、癸基三甲基铵、己基三乙基铵、4-甲基苄基三甲基铵及其类似物。
所指酸加成盐是这样的物质,它上面的阴离子是一个农学上可接受的阴离子,如氯、溴、硫酸根、硝酸根、高氯酸根、乙酸根、草酸根及其类似
物。
在一个优选实例中,农学上可接受的盐包括钠、钾、铵、烷基铵、氯化物和硫酸盐所成的盐。
本发明的1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑或它们的前体可通过对3-取代-5-硫代-1H-1,2,4-三唑进行硫烷基化(S-烷基化)而制得,S-烷基化是在一种对反应物显惰性的溶剂或稀释剂存在、且有时有以下式表示的化合物作酸清除剂存在下进行,
Z-R′-X Ⅱ
其中,R′和X如在式Ⅰ中所定义的,Z是一个很好的离去基团。离去基团可参见Roperts and Caserio,“Basic Principles of Organic Chemistry”,W.A.Benjamin Inc.,NewYorK,1965,P.290。离去基团的例子包括卤代基(氯、溴或碘)、烷基磺酸根、芳基磺酸根或烷基硫酸根。
适用于上述烷基化过程的溶剂或稀释剂包括(但不限于)甲醇、乙醇、醋酸乙酯、四氢呋喃、二甲基甲酰胺和乙腈及其类似物。
适用于上述过程的酸清除剂,如三乙胺或二异丙基乙基胺,可在烷基化过程中加入,如有必要,3-取代-5-硫代-1H-1,2,4-三唑可用一种酸清除剂(如氢化钠、氢氧化钠及其类似物)进行预处理。
通常,起始物料的当量摩尔量取为0.01至5摩尔,上述过程在0℃至150℃间进行约5分钟至2天。优先选择的是,起始物料浓度从0.1摩尔至1摩尔,反应在20℃至90℃进行。
可能需要对上述过程作些改进,以特定地调节5-取代基的官能度。这样的改进对专业人员是熟知的。
由上述过程制得的3-取代-5-取代-1H-1,2,4-三唑随后与下式表示的化合物反应,
其中,Hal是卤素(氯、溴、碘),反应是在一种适用的酸清除剂存在下、且在一种根据需要选用的合适的酰化催化剂存在下进行的。
适宜于这个过程的酸清除剂包括叔胺,如三乙胺和吡啶及其类似物。
适宜的酰化催化剂包括叔胺如4-二乙胺基吡啶、4-吡咯烷基吡啶、三乙胺、吡啶及其类似物。
通常,当采用了酰化催化剂时,它在反应混合物中的量大约是在0.001至0.25摩尔当量之间(以起始物料为准计算)。
通常,以摩尔当量表示的起始物料总浓度约为0.01摩尔至5摩尔,以上过程在0℃至150℃之间进行5分钟至约2天。较好的起始物料浓度是在约0.1摩尔至1摩尔之间,反应温度约为20℃至约90℃。
式Ⅱ表示的化合物可从已知的前体用已知的方法制得。
用作反应起始物料的3-取代-5-硫代-1H-1,2,4-三唑可从已知的前体用已知的方法(如在实施例1中描述的那样)制备。
当制备出式Ⅰ表示的化合物后,本发明的盐类可按本技术领域认可的任何方便方法制备,如用一种金属氢氧化物、金属氢化物或一种胺或铵盐(如卤化铵、氢氧化铵或烷氧化铵)与它的游离酸反应,或用一种季铵盐如氯化铵、溴化铵、硝酸铵或其类似物在恰当的溶剂中与本发明的金属盐反应。当金属氢氧化物被用作反应剂,适用的溶剂包括水、甘醇二甲醚、二噁烷、四氢呋喃、甲醇、乙醇、异丙醇及其类似物。当金属氢化物被用作反应剂时,适用的溶剂包括非羟基溶剂,如二噁烷、甘醇二甲醚、四氢呋喃、乙醚,还包括烃类如甲苯、二甲苯、己烷、戊烷、庚烷、辛烷、二甲基甲酰胺及其类似物。当用胺作为反应剂时,适用的溶剂包括醇,如甲醇或乙醇,包括烃类如甲苯、二甲苯、己烷及其类似物、四氢呋喃、甘醇二甲醚、二噁烷或水。当铵盐被用作反应剂时,适用的溶剂包括水、醇如甲醇或乙醇、甘醇二甲醚、四氢呋喃或其类似物。当所用铵盐不是羟基盐或醇盐时,则通常要用另外一种碱,如钾或钠的氢氧化物、氢化物或醇盐。对溶剂的特定的选择要取决于起始物料与生成的盐或这些盐的浆料的相对溶解度,而不取决于用于制取这些盐的反应剂的溶液。通常,起始反应剂以等当量使用,成盐反应在约0℃至约100℃进行,优先选用的是在大气压和室温下进行反应。
本发明的酸加成盐可通过本领域认可的任何一种方便方法来制备,如用氢氯酸、氢溴酸、硫酸、硝酸、磷酸、乙酸、丙酸、苯甲酸或其它适宜的酸在适宜的溶剂中与具有碱性官能团的一种本发明化
合物反应。适宜的溶剂包括水、醇、醚、酯、酮、卤代烷及其类似物。对溶剂的特定选择将取决于起始物料与生成的盐的或这些盐的浆料相对溶解度,而不取决于用于制取这些盐的反应剂的溶液。通常,初始物料以等当量使用,其成盐反应在约-100℃至约100℃内进行,较好的是在室温附近进行。
以下实施例将进一步说明本发明,但不对本发明有任何限制。表1中,列出了依本发明的典型的1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑。
这些化合物的结构已由NMR谱、由IR谱和/或元素分析证实。
这些化合物的好几种制剂的具体描述见于表Ⅰ之后。(表Ⅰ见文后)
实例A
3-叔丁基-5-硫代-1H,1,2,4-三唑的制备
在一个5升的圆底烧瓶中,500克(5.49摩尔)氨基硫脲悬浮在2升四氢呋喃(THF)中,并用冰浴将它冷却至10℃的内温,用时30分钟向该悬浮液中加入694克(5.76摩尔)三甲基乙酰氯,将由于放热而引起的温升控制在40℃以下。然后用30分钟时间加入482克(6.04摩尔)50%的NaOH水溶液,并控制放热使温度低于50℃。此后,移去冷却浴并搅拌混合物2小时。对该混合物加热并蒸馏除去600毫升THF,此后用时90分钟向它添加由1500毫升水和835克含水50%NaOH所形成的一个溶液。在此期间内,继续除去THF,直至使内部温度升到80℃。之后该混合物继续回流三个小时,然后将它冷却至室温,再把它转移到一个12升的分液漏斗中。向它加入3kg冰和1500ml THF,然后用1500毫升浓盐酸使该混合物变成酸性的。分离出水相,并在弃置之前用2升醋酸乙酯萃取。之后有机层用2升盐水洗涤,并用500克硫酸镁干燥,再在真空下浓缩至得到698克白色固体状3-叔丁基-5-硫代-1H-1,2,4-三唑,熔点(m.p.)20℃。
实施例1
1-二甲胺基甲酰基-3-叔丁基-5-(1,3-二噁烷-2-基-甲硫基)-1H-1,2,4-三唑(化合物3)的制备
在矿物油中的1.4克60%氢化钠(35毫摩尔)用己烷洗涤两次,然后悬浮于10毫升二甲基甲酰胺(DMF)中。将由5克(31.8毫摩尔)3-叔丁基-5-硫代-1H-1,2,4-三唑溶于10毫升DMF所形成的溶液缓慢地加入到上述悬浮液中,并在室温下进行搅拌直至停止放出氢,此后,加入5.3克(31.7毫摩尔)2-溴甲基-1,3-二氧戊环,并回流进行反应3小时。减压移去溶剂,并将得到的混合物在二氯甲烷和水之间进行分配。分离出有机层,在硫酸镁上干燥,浓缩。用乙醚/己烷进行研制(Trituration),得到7.5克固体的3-叔丁基-5-(1,3-二氧戊环-2-基-甲硫基)-1H-1,2,4-三唑。
7克(28.8毫摩尔)3-叔丁基-5-(1,3-二氧戊环-2-基-甲硫基)-1H-1,2,4-三唑、2.8毫升(30.5毫摩尔)二甲胺基甲酰氯、8毫升(57毫摩尔)三乙胺和0.5克(4.1毫摩尔)4-二甲胺基吡啶一起溶于50毫升四氢呋喃(THF)中。回流该混合物四小时,在负压下浓缩后将它在二氯甲烷和稀盐酸中进行分配。分离出有机层,用硫酸镁干燥,过滤并浓缩。用硅胶色谱法(乙醚/己烷做展开溶剂)得到提纯的1-二甲胺基甲酰基-3-叔丁基-5-(1,3-二氧戊环-2-基-甲硫基)-1H-1,2,4-三唑,它为一油状物。
实施例2
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-2-基-甲硫基)-1H-1,2,4-三唑(化合物4)的制备
将5克(31.8毫摩尔)3-叔丁基-5-硫代-1H-1,2,4-三唑和5克(30.5毫摩尔)2-氯甲基吡啶盐酸盐
悬浮于50毫升THF中并回流3小时。该混合物冷却至10℃并用50毫升己烷稀释。将生成的固体滤出,得到10克3-叔丁基-5-(吡啶-2-基-甲硫基)-1H-1,2,4-三唑二氢氯化物,熔点为190~192℃。
将10克3-叔丁基-5-(吡啶-2-基-甲硫基)-1H-1,2,4-三唑二氢氯化物、0.5克(4.1毫摩尔)4-二甲胺基吡啶、10克(100毫摩尔)三乙胺、3.5克二甲胺基甲酰氯和100毫升THF一起回流2小时。将该混合物进行减压浓缩,再在醚和水间分配,有机层用盐水洗涤,用硫酸镁干燥、过滤、减压蒸去溶剂,得到1-二甲胺基甲酰
基-3-叔丁基-5-(吡啶-2-基-甲硫基)-1H-1,2,4-三唑,为一种油状物。
实施例3
1-二甲胺基甲酰基-3-叔丁基-5-(呋喃-2-基-甲硫基)-1H-1,2,4-三唑(化合物13)的制备
5克(31.8毫摩尔)3-叔丁基-5-硫代-1H-1,2,4-三唑溶解于50毫升醋酸乙酯和6毫升(34毫摩尔)二异丙基乙基胺中。向它加入3.7克工业纯的2-氯代甲基呋喃(约35毫摩尔),搅拌该混合物18小时。用水和盐水洗涤该混合物,用硫酸镁干燥、减压浓缩并用乙醚/己烷研制,得到3-叔丁基-5-(呋喃-2-基-甲硫基)-1H-1,2,4-三唑,它为一种固体。
将3-叔丁基-5-(呋喃-2-基-甲硫基)-1H-1,2,4-三唑与二甲胺基甲酰氯反应,反应实际按描述于实施例1的方法进行,得到1-二甲胺基甲酰基-3-叔丁基-5-(呋喃-2-基-甲硫基)-1H-1,2,4-三唑,它为一油状物。
实施例4-11
如下列出之化合物6-12和14是从对应的卤代甲基杂环并用实施例中给出的基本方法来制得的。
(表见文后)
实施例12~15
如下面所列的化合物1,2,5和17是利用适当的卤代甲基杂环用与实施例2基本相同的方法制备的。
(表见文后)
实施例16和17
如下面所列的化合物15和16,是利用适当的卤代甲基杂环并以三乙胺代替二异丙基乙胺,使用与实施例3基本相同的方法制备的。
(表见文后)
意外地发现,本发明的许多化合物比最接近的已知化合物显示出更强的杀虫活性。另外;这些化合物尤其对蚜虫有杀虫活性,它们可以用于保护作物,同时对于益虫没有影响。这样,这些化合物尤其适用于综合病虫害防治。益虫包括传粉昆虫(如密蜂)(Apismellifera);捕食性昆虫(如瓢虫)(Hippodamia convergons);和寄生性昆虫(如uga wasp(Uga menoni)。
具体地说,本发明的化合物具有抗同翅目类吸食性昆虫,尤其是蝉(Suporder;Auchenorrhyncha)和蚜虫(Suborder,Sternorrhyncha)的活性。例如,本发明的1-二甲胺基甲酰基-3-取代-5-取代-1H-1,2,4-三唑表示出在约1~21.0ppm的浓度下具有抗桃蚜活性。还可以观察到抗土豆和苹果叶蝉的活性。因此,本发明的化合物表面出前所未有的进展。
根据本发明杀虫化合物的初始杀虫活性,它们可以低剂量用于控制虫害。施用剂量取决于各种因素,例如所用的化合物、虫害的类别所用的制剂、感染虫害的作物的状况以及盛行的气候条件。通常,为了防治农业及园艺上的虫害,有效物质的使用剂量可以是每公顷约10g~约~1000g,最好是每公顷约50g~250g。
实际应用时,本发明化合物可以组合物或制剂形式使用。在这些组合物及制剂中,有效物质是与常规的惰性(即植物可以耐受和/或无杀虫作用)的稀释剂或增充剂(如可用于常规组合物或制剂中的一类固体或液体载体物质)相混合的。如果需要的话,还可混入表面活性剂、稳定剂、消泡剂、防漂剂等辅助剂。本发明的组合物及制剂的实例有水溶液及分散液、油溶液及油分散液、糊剂、粉剂、可湿性粉剂、乳剂、可流动剂、粒剂、毒饵、转化乳剂(invert emulsions)、气溶胶组合物及熏蒸灶(fumigatingcandles)。组合物和制剂是按已知方法制造的,例如,可将有效化合物搀入常规的可分散液体稀释载体和/或可分散固体载体中,还可按需要使用载体助剂,例如常规的表面活性剂,包括乳化剂和/或分散剂;因此,例如当使用水作稀释剂时,就可以加入有机溶剂作助溶剂。
本发明的有效化合物可以单用;也可以混合物形式使用,这种混合物为一种本发明的化合物与另一种本发明的化合物和/或与这样的固态和/或液态可分散载体和/或与其它已知的适宜相容药剂的混合物,上述适宜的有效药剂尤其是植物保护剂,如其它杀节肢动物剂(arthopodicides),杀线虫剂、杀真菌剂、杀啮齿动物剂(rodenticides)、除莠剂、肥料、生长调节剂、增效剂等;如果需要的话,本发明的有效化合物也可以组成特殊的药剂而用于特殊的用途,这些药剂有备用的溶液、乳液、悬浮液、粉剂、糊剂及粒剂。
在本发明的组合物中,有效化合物的含量一般大约在约0.0001~95%(重量)之间。适用于直接施用的混合物中有效化合物的含量大体上占该混合物重量的约0.0001~95%(重量)之间。适用于直接施用的混合物中有效化合物的含量大体上占该混合物重量的约0.0001%~5%,最好占约0.001%~3%。
本发明包括全部的组合物,其中含有常规的可分散性载体与有效化合物的混合物,其中的有效化合物的量能满足使用要求;所说的可分散性载体,例如有(1)磨细的可分散惰性固体载体,和/或(2)可分散液体载体,如惰性有机溶剂和/或水,最好包括能有效地起到表面活化作用的量的载体媒介物助剂(例如表面活性剂,如乳剂和/或分散剂)。
有效化合物可按常用方法以喷雾形式使用,例如常规的高加仑数水喷雾、低加仑数喷雾、超低量喷雾、空气喷雾、气化喷雾及喷粉。
此外,本发明还涉及有选择地杀灭、抵抗或控制害虫的方法,该方法包括:至少向(a)这类害虫和/或(b)这类害虫的滋生处(即要保护的地方,例如向生长中的作物或向要种植作物的区域)中的一处施用相应抵抗或有毒量(即杀虫有效量)的本发明的特定有效化合物,或其与上述的载体媒介物的混合物。
当然,可以理解的是,与载体媒介物混用的特定有效化合物的浓度取决于下列一些因素,例如:设备类型、施用方法、待处理区域、要防治的害虫种类及虫害程度。因此,在特殊情况下,有效化合物使用浓度可以在前述浓度范围之外。
除上述成分而外,本发明制剂还含有其它该类制剂常用的物质。例如,润滑剂如硬脂酸钙或硬脂酸镁可加入可湿性粉剂或配制的要成粒的混合物中。而且,可加入“粘结剂”如聚乙烯醇纤维素衍生物或其它胶状物质如酪素,以增加昆虫在被保护表面上的粘性。
本发明的化合物还可以于防治种子中的害虫,一般可将有效量的化合物施用于要处理的种子的表面。这种处理可按照各种本技术领域中常用的方法进行,例如:拌浆、浸泡、撒粉、喷雾等。
本发明组合物及制剂中也可以含有已知的杀虫化合物。这样可以扩大这些制剂的活性谱,并且可能产生协同效应,下列已知的杀虫、杀真菌、杀螨化合物适用于这种复合制剂:
杀虫剂,例如:
1.氯代烃,例如2,2,-双(对氯苯基)-1,1,1-三氯乙烷、六氯环氧八氢二甲桥萘;
2.甲氨酸酯类,如N-甲基甲氨酸1-萘酯;
3.二硝基酚类,例如2-甲基-4,6-二硝基苯基-3,3-二甲基丙烯酸酯和2-(2-丁基)-4,6-二硝基苯基-3,3-二甲基丙烯酸酯;
4.有机磷化合物,例如二甲基-2-甲氧羰基-1-甲基乙烯基磷酸酯、O,O-二乙基-O-对硝基苯基硫代磷酸酯,O,O-二甲基二硫代磷酰乙酸N-单甲基酰胺;
5.二苯硫醚类,例如对氯苄基硫醚或对氯苯硫醚及2,4,4′-5-四氯二苯硫醚;
6.二苯基磺酸酯类,例如对氯苯基苯磺酸酯;
7.甲基甲醇类,例如4,4-二氯-1-三氯甲基二苯基甲醇;
8.喹喔啉化合物,如甲基喹喔啉二硫代碳酸酯;
9.脒类,如N′-(4-氯-O-甲苯基)-N,N-二甲基甲脒;
10.拟除虫菊酯,如丙烯除虫菊;
11.生物制剂,如苏云金芽孢杆菌制剂;
12.有机锡化合物,例如氢氧化三环己基锡;
杀真菌剂,如
13.有机汞化合物,如乙酸苯基汞、氰基胍基甲基汞;
14.有机锡化合物,例如氢氧化三苯锡及乙酸三苯锡;
15.亚烷基双二硫代甲氨酸盐,例如亚乙基双硫代甲氨酸锌和亚乙基双硫代甲氨酸锰等;
16.2,4-二硝基-6-(2-辛基-苯基巴豆酸酯)、1-双(二甲氨基)磷酰-3-苯基-5-氨基-1,2,4-三唑、6-甲基喹喔啉-2,3-二硫代碳酸酯、1,4-二硫代蒽醌-2,3-二甲腈、N-三氯甲硫基苯邻二甲酰亚胺、N-三氯甲硫基四氢苯邻二甲酰亚胺、N-(1,1,2,2-四氯乙硫基)四氢苯邻二甲酰亚胺、N-二氯氟甲硫基-N-苯基-N′-二甲基磺酰二酰胺以及四氯异邻苯二甲腈。
对本发明化合物的生物活性进行了鉴定。在测定本发明化合物的叶面用药杀虫活性时,采用了下列试验方法。
先配制600ppm的试验溶液,方法是将试验化
合物溶于溶剂(丙酮∶二甲醇,1∶1);加入表面活性剂,再加水,得到5∶5∶90的丙酮∶甲醇∶水体系。所用表面活性剂是一种烷基芳基聚醚醇(Triton
X-155,表面活性剂,Rohm & Hass公司产品,Philadelphia,PA)与改性的邻苯二甲酸甘油烷基树脂(Triton
B-1956表面活性剂,Rohm & Hass公司产品,Philadelphia,PA)的1∶1混合物,此化合物的用量为每100加仑试验溶液1盎司。
用水和表面活性剂将600ppm试验溶液稀释,得到一系列类似的溶液,其浓度为150、38、10、2.5、0.6、0.15和0.38ppm。但并非全部化合物都以每一种上述浓度进行试验。化合物的试验浓度是这样选取的,即所取浓度最有可能使给定化合物对于给定的害虫的施用量不同时,能产生不同的杀虫效果。
使用下列一种或多种害虫,进行了初步的杀虫效果评价:
(表见文后)
在用墨西哥瓢虫和南方粘虫进行的试验中,用试验溶液喷雾将种在3英寸小罐中的利马豆(Phaseolns limensis)品种,Woods′Prolific)小苗淋透。干后,将各植株放入塑料箱(和7.5英寸,宽5.25英寸,深3.75英寸)中。然后在每箱内引入10只第三龄墨西哥瓢虫幼虫或南方粘虫的幼虫。再盖上有筛眼状通风孔的盖子将箱子封好。
在暴露期间,温度为80°F,塑料箱置于开放式搁架上,有连续荧光照射,所有测量处理照常进行。需要时给植株浇水;如果在处理无效或在未处理的植株或对照植株的情况下,植株被害虫完全吃掉,则更换以未处理的植株,处理后48小时,对每种试验化合物和喷雾浓度测定死亡百分率。
在杀螨试验中,将盛放有虫害的大豆(Phaseolus limeanus)叶的圆盘(直径1.25英寸)(其中大约50只螨)放在置于潮湿棉花片上的培养皿盖中。再利用旋转盘用试验溶液向大豆叶喷雾至湿透,静置24小时,然后测定杀螨率。
在杀蚜虫试验中,将含有约50只蚜虫的受虫害的broccoli(Brassica olerscea italica)叶片放在置于潮湿棉花片上的培养皿盖上。然后利用旋转盘用试验溶液向叶面喷雾至湿透,静置24小时,然后测定杀死百分率。
在杀棉象甲(boll weevil)试验中,将10只成熟的甲象放于含有小块苹果的0.5品脱的玻璃陶瓷罐中。用周围有螺丝固定的玻璃纤维筛网将象甲封在罐中。然后用旋转盘向罐中喷试验溶液;直接通过筛网喷入罐中。48小时后,测量杀死百分率。
将以此方法获得的死亡率数据在对数概率纸上作图。按照死亡率数据的作图点描出尽量平滑的曲线,据此曲线确定出对应于50%死亡率(LC50)估计浓度。
叶面施药杀虫试验的结果列于表2。注意本发明的某些化合物具有抗蚜虫的选择性。
(表2见文后)
在本发明化合物对蝉的杀虫活性研究中,对下列害虫进行初步研究。
在杀土豆叶蝉试验中,使装在5cm培养皿中的不同尺寸的fava bush bean(Vicia fava)的叶用600ppm的试验溶液浸泡后,空气干燥,再将其置于衬以湿Gelman滤片(每片1ml水)的直径为5cm的紧密封闭的培养皿。小心地将土豆叶蝉若虫(每个皿5只若虫)扫进该皿中,然后将其盖好。处理3天后,目测杀死百分率。
在杀苹果叶蝉的试验中,用苹果(Malus Svlvestris“Mc Intosh”)叶代替fava bean叶,以相同方法进行试验。
在绿色稻叶蝉和深黄色稻株蝉的试验中,用600ppm的试验溶液浸泡稻苗,空气干燥后置于玻璃管中。将成熟的昆虫(每管中5只)放入装有处理的稻苗的玻璃管中,然后用棉塞盖好。处理后48小时,目测杀死百分率。
所得结果列于表3中。
(表3见文后)
通过上述说明和实例,本发明将被充分地理解,但是对本发明不起到任何限制,各种改进和变化都包括在后续权利要求所限定的本发明范围之内。
表1
序号 W R1X 熔点℃
1 叔丁基 -CH2- 100-102
2 叔丁基 -CH2- 47-48
3 叔丁基 -CH2- 油
4 叔丁基 -CH2- 油
5 叔丁基 -CH2- 油
6 叔丁基 -CH2- 油
7 叔丁基 -CH2- 146-147
8 叔丁基 -CH2- -CH(OCH3)2油
9 叔丁基 -CH2- -CH(OCH2CH3)2油
表1(续)
序号 W R1X 熔点℃
11 ″ -CH2- -C(CH3)(OCH3)2油
12 ″ -CH2- 88-90
13 ″ -CH2- 油
14 ″ -CH2- 油
15 ″ -CH2- 油
16 ″ -CH2- 油
17 ″ -CH2- 117-121
表2
叶面杂虫评价1估计值LC50
序号 SAW MBB GPA TSM BW
1 460 75 1.1 >600 300
2 300 138 4.7 >600 162
3 24 <38 1.5 170 62
4 150 24 3.1 81 150
5 >600 115 5.4 560 >600
6 >600 52 2.6 340 >600
7 360 - 21.0 >600 150
8 600 38 1.4 50 31
9 >600 52 2.0 108 >600
10 >600 23 4.3 >600 500
11 >600 >600 5.0 >600 150
12 78 4.2 <2.5 313 500
13 78 5 0.95 400 70
14 >600 52 3.3 355 >600
15 150 150 9.2 >600 150
1杀死上述害虫的50%的浓度(ppm)(LC50)
化合物 名称 原料上 反应 时间
序号 的卤素 温度
6 1-二甲胺基甲酰基-3-叔丁基-5- Br 回流 5小时
(四氢吡喃-2-基-甲硫基)-1H-
1,2,4-三唑
7 1-二甲胺基甲酰基-3-叔丁基-5- Cl 100℃ 5小时
(噁唑烷酮-5-基-甲硫基)-1H-
1,2,4-三唑
8 1-二甲胺基甲酰基-3-叔丁基-5- Br 60℃ 3小时
(2,2-二甲氧基乙硫基)-1H-
1,2,4-三唑
9 1-二甲胺基甲酰基-3-叔丁基-5- Br 80℃ 5小时
(2,2-二乙氧基乙硫基)-1H-
1,2,4-三唑
10 1-二甲胺基甲酰基-3-叔丁基-5- Cl 70℃ 4小时
(3,5-二甲基-异噁唑-4-基-甲硫基)-1H-
1,2,4-三唑
11 1-二甲胺基甲酰基-3-叔丁基-5- Br 80℃ 4小时
(2,2-二甲氧基-丙硫基)-1H-
1,2,4-三唑
12 1-二甲胺基甲酰基-3-叔丁基-5- Br 回流 4小时
(1,3-二烷-2-基-甲硫基)-1H
-1,2,4-三唑
14 1-二甲胺基甲酰基-3-叔丁基-5- Cl 80℃ 4小时
(5,5-二甲基-1,3-二烷-2-基-
甲硫基)-1H-1,2,4-三唑
化合物 名称 原料上 时间
序号 的卤素
1 1-二甲胺基甲酰基-3-叔丁基-5- Cl 6小时
(1,2,4-三唑-1-基-甲硫基)-1H- (盐酸盐)
1,2,4-三唑
2 1-二甲胺基甲酰基-3-叔丁基-5- Cl 2小时
(吡啶-3-基-甲硫基)-1H- (盐酸盐)
1,2,4-三唑
5 1-二甲胺基甲酰基-3-叔丁基-5- Cl 18小时
(吡啶-4-基-甲硫基)-1H- (盐酸盐)
1,2,4-三唑
17 1-二甲胺基甲酰基-3-叔丁基-5- Cl 18小时
(喹啉-2-基-甲硫基)-1H- (盐酸盐)
1,2,4-三唑
化合物 名称 原料上 反应 时间
序号 的卤素 温度
15 1-二甲胺基甲酰基-3-叔丁基-5- Cl 回流 4小时
(吡嗪-2-基-甲硫基)-1H-
1,2,4-三唑
16 1-二甲胺基甲酰基-3-叔丁基-5- Cl 回流 18小时
(苯二甲酰亚氨基-甲硫基)-1H-
1,2,4-三唑
代码 通用名 拉丁名
SAW 南方粘虫 Spodoptera eridania
MBB 墨西哥豆瓢虫 Epilachna varivestis
GPA 桃蚜 Myzus persicae
TSM 二点叶螨 Tetranychus urticae
BW 棉铃象 Anthonomus grandis
通用名 拉丁名
土豆叶蝉 Empoasca fabae
苹果叶蝉 Empoasca maligna
绿稻叶蝉 Nephotettix cincticeps
深黄色稻叶蝉 Nilaparvata lugens
表3
化合物1杀蝉的0天残留效果
害虫 杀死百分率(600ppm)
土豆叶蝉 100
苹果叶蝉 100
绿色稻叶蝉 100
深黄色稻株蝉 100
Claims (11)
2、依权利要求1的组合物,其中
X为三唑基,二氧戊环基,二噁烷基或呋喃基。
3、依权利要求1的组合物,其中化合物选自
1-二甲胺基甲酰基-3-叔丁基-5-(1,2,4-三唑-1-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-3-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(1,3-二氧戊环-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-4-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(四氢吡喃-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2-噁唑烷酮-5-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2,2-二甲氧基-乙基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2,2-二乙氧基-乙基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(3,5-二甲基-异噁唑-4-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2,2-二甲氧基-丙基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(1,3-二烷-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(呋喃-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(5,5-二甲基-1,3-二噁烷-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡嗪-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(苯二(甲)酰亚氨基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(喹啉-2-基-甲基硫基)-1H-1,2,4-三唑,
4、权利要求1的组合物在昆虫控制中的应用,其中包括将昆虫与权利要求1的组合物接触。
5、依权利要求4的应用,其中
X为三唑基,二氧戊环基,二噁烷基或呋喃基。
6、依权利要求5的应用,其中本发明的化合物选自:
1-二甲胺基甲酰基-3-叔丁基-5-(1,2,4-三唑-1-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-3-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺甲酰基-3-叔丁基-5-(1,3-二氧戊环-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡啶-4-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(四氢吡喃-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2-噁唑烷酮-5-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2,2-二甲氧基-乙基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2,2-二乙氧基-乙基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(3,5-二甲基-异噁唑-4-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(2,2-二甲氧基-丙基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(1,3-二烷-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(呋喃-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(5,5-二甲基-1,3-二烷-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(吡嗪-2-基-甲基硫基)-1H-1,2,4-三唑,
1-二甲胺基甲酰基-3-叔丁基-5-(苯二(甲)酰亚氨基-甲基硫基)-1H-1,2,4-三唑和,
1-二甲胺甲酰基-3-叔丁基-5-(喹啉-2-基-甲基硫基)-1H-1,2,4-三唑,
7、依权利要求4的应用,其中昆虫属同翅目。
8、依权利要求4的应用,其中昆虫为蚜虫(胸缘类)。
9、依权利要求4的应用,其中昆虫为hoppers(头缘类)。
10、依权利要求4的应用,其中化合物用量为约10-约5000g/ha。
11、依权利要求4的应用,其中化合物用量为约50-约2500g/ha。
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US3973028A (en) * | 1973-10-18 | 1976-08-03 | Gulf Oil Corporation | 1-Dimethylcarbamyl-3-branched alkyl-1,2,4-triazol-5-yl-(N-substituted) sulfonamides and use as insecticides |
GB1510636A (en) * | 1974-07-08 | 1978-05-10 | Boots Co Ltd | Substituted 1,2,4-triazoles and insecticidal compositions and uses of them |
US4038387A (en) * | 1974-10-10 | 1977-07-26 | Gulf Oil Corporation | 1-dimethylcarbamyl-3-branched alkyl-1,2,4-triazol-5-yl-(n-substituted) sulfonamides and their use as insecticides |
IN145063B (zh) * | 1975-12-01 | 1978-08-19 | Union Carbide Corp | |
US4066774A (en) * | 1976-03-01 | 1978-01-03 | Gulf Oil Corporation | Method of killing insects employing a certain triazole |
US4160839A (en) * | 1976-03-01 | 1979-07-10 | Gulf Oil Corporation | Carbamyltriazole insecticides |
US4220790A (en) * | 1977-10-17 | 1980-09-02 | Gulf Oil Corporation | 1-N,N-Dimethylcarbamyl-3-tert.butyl-5-methylthio-1,2,4-triazole |
US4291043A (en) * | 1978-09-06 | 1981-09-22 | Ciba-Geigy Corporation | 1-N,N-dimethylcarbamoyl-3(5)-alkyl-5(3)-alkylthioalkylthio-1,2,4-triazoles, a process for their manufacture, compositions which contain them and their use in pest control |
DE3021232A1 (de) * | 1979-06-07 | 1980-12-11 | Ciba Geigy Ag | 1,2,4-triazole mit pestizider wirkung |
EP0029407A3 (de) * | 1979-08-21 | 1981-08-26 | Ciba-Geigy Ag | 1-N,N-Dimethylcarbamoyl-3(5)-alkyl-5(3)-alkoxyalkylthio-1,2,4-triazole, Verfahren zu ihrer Herstellung, diese Verbindungen enthaltende Mittel und ihre Verwendung zur Bekämpfung von Schädlingen sowie ihre Ausgangsprodukte und deren Herstellung |
DE3031191A1 (de) * | 1979-08-21 | 1981-03-12 | CIBA-GEIGY AG, CH 4002 Basel | 1,2,4-triazole mit pestizider wirkung |
US4255435A (en) * | 1980-01-04 | 1981-03-10 | The Boots Company Limited | Triazole compounds |
FR2514760A1 (fr) * | 1981-10-16 | 1983-04-22 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique comportant un groupement alcoylthio carbonyle, leur preparation, leur application a la lutte contre les parasites des vegetaux, des animaux et des locaux, et les compositions les renfermant |
EP0140194B1 (en) * | 1983-10-18 | 1989-02-01 | Sumitomo Chemical Company, Limited | Carbamoyltriazoles, and their production and use |
US4742072A (en) * | 1985-07-25 | 1988-05-03 | Rohm And Haas Company | 1-dimethylcarbamoyl-3-t-butyl-5-substituted-1H-1,2,4-triazoles |
CA1293505C (en) * | 1985-07-25 | 1991-12-24 | Richard Martin Jacobson | 1-dimethylcarbamoyl-3-substituted-5-substituted-1h-1, 2,4-triazoles |
US5015652A (en) * | 1988-04-04 | 1991-05-14 | Rohm And Haas Company | 1-dimethylcarbamoyl-3-substituted-5-substituted-1H-1,2,4-triazoles |
-
1988
- 1988-04-15 US US07/181,872 patent/US4970224A/en not_active Expired - Lifetime
-
1989
- 1989-04-03 BR BR898901561A patent/BR8901561A/pt not_active IP Right Cessation
- 1989-04-03 CA CA000595518A patent/CA1330996C/en not_active Expired - Fee Related
- 1989-04-10 NZ NZ228679A patent/NZ228679A/en unknown
- 1989-04-11 EG EG11889A patent/EG20070A/xx active
- 1989-04-12 ZA ZA892664A patent/ZA892664B/xx unknown
- 1989-04-13 TR TR89/0316A patent/TR23745A/xx unknown
- 1989-04-13 AU AU32798/89A patent/AU623386B2/en not_active Ceased
- 1989-04-14 ES ES89303737T patent/ES2125849T3/es not_active Expired - Lifetime
- 1989-04-14 DE DE68928885T patent/DE68928885T2/de not_active Expired - Fee Related
- 1989-04-14 AT AT89303737T patent/ATE174911T1/de not_active IP Right Cessation
- 1989-04-14 IL IL89959A patent/IL89959A/xx not_active IP Right Cessation
- 1989-04-14 HU HU891857A patent/HU206604B/hu not_active IP Right Cessation
- 1989-04-14 KR KR1019890004939A patent/KR0122082B1/ko not_active IP Right Cessation
- 1989-04-14 EP EP89303737A patent/EP0337815B1/en not_active Expired - Lifetime
- 1989-04-14 DK DK181089A patent/DK181089A/da not_active Application Discontinuation
- 1989-04-14 JP JP1095068A patent/JP2779949B2/ja not_active Expired - Lifetime
- 1989-04-14 PT PT90281A patent/PT90281B/pt active IP Right Grant
- 1989-04-15 CN CN89102293A patent/CN1024985C/zh not_active Expired - Fee Related
-
1999
- 1999-03-09 GR GR990400729T patent/GR3029638T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
DK181089D0 (da) | 1989-04-14 |
AU623386B2 (en) | 1992-05-14 |
ZA892664B (en) | 1989-12-27 |
KR900016160A (ko) | 1990-11-12 |
PT90281B (pt) | 1994-07-29 |
TR23745A (tr) | 1990-08-01 |
ES2125849T3 (es) | 1999-03-16 |
KR0122082B1 (ko) | 1997-11-13 |
CN1037340A (zh) | 1989-11-22 |
BR8901561A (pt) | 1989-11-21 |
DK181089A (da) | 1989-10-16 |
NZ228679A (en) | 1992-05-26 |
IL89959A0 (en) | 1989-12-15 |
US4970224A (en) | 1990-11-13 |
CA1330996C (en) | 1994-07-26 |
EP0337815B1 (en) | 1998-12-23 |
JP2779949B2 (ja) | 1998-07-23 |
AU3279889A (en) | 1989-10-19 |
DE68928885T2 (de) | 1999-05-20 |
EG20070A (en) | 1997-12-31 |
IL89959A (en) | 1993-04-04 |
GR3029638T3 (en) | 1999-06-30 |
ATE174911T1 (de) | 1999-01-15 |
EP0337815A1 (en) | 1989-10-18 |
DE68928885D1 (de) | 1999-02-04 |
HU206604B (en) | 1992-12-28 |
PT90281A (pt) | 1989-12-29 |
JPH01311069A (ja) | 1989-12-15 |
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