CN1065272A - 1-环己基二丁基锡-1，2，4-三氮唑合成方法 - Google Patents
1-环己基二丁基锡-1，2，4-三氮唑合成方法 Download PDFInfo
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- CN1065272A CN1065272A CN 91101933 CN91101933A CN1065272A CN 1065272 A CN1065272 A CN 1065272A CN 91101933 CN91101933 CN 91101933 CN 91101933 A CN91101933 A CN 91101933A CN 1065272 A CN1065272 A CN 1065272A
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- -1 1-cyclohexyl dibutyl tin-1,2,4-triazole Chemical compound 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 10
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- 238000010992 reflux Methods 0.000 claims description 8
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- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- NGQQUXXTDZADNX-UHFFFAOYSA-N 2,3,4,5-tetrachlorofuran Chemical class ClC=1OC(Cl)=C(Cl)C=1Cl NGQQUXXTDZADNX-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
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- SXLXYDPVHCAULH-UHFFFAOYSA-M dibutyl(cyclohexyl)stannanylium;chloride Chemical compound CCCC[Sn](Cl)(CCCC)C1CCCCC1 SXLXYDPVHCAULH-UHFFFAOYSA-M 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明属有机农药杀螨杀菌剂类，合成了一种同
时具有杀螨杀菌效果的有机锡化合物：1-环己基二
丁基锡-1，2，4-三氮唑((CH3CH2CH2CH2)2(环
-C6H13)
Description
本发明属有机农药杀螨、杀菌剂类。
农作物的病虫害是多种多样的，不同的作物有不同的病、虫害，同一种作物往往又会同时发生病害和虫害。因此寻找一种广谱性的新药剂及其生产方法，通过施用一种药剂能同时防治病害和虫害，以达到防虫治病的效果，这无疑会减少农药的使用次数及用量，节约劳动力，降低农业成本，避免农药使用上可能出现的混乱，同时还可减少农药对环境的污染。
本发明的目的在于提供一种既可杀螨，又可杀菌的新的化学药剂及合成方法。本发明是用氯代正丁烷、四氯化锡、氯代环己烷为基本原料。首先将氯代正丁烷制成格氏试剂后与四氯化锡反应制成四丁基锡，再与四氯化锡重排成二丁基二氯化锡，然后与氯代环己烷制成的格氏试剂反应得到环己基二丁基氯化锡，最后用氢氧化钠碱解成氧化物，与1H-1，2，4-三氮唑缩合成1-环己基二丁基锡-1，2，4-三氮唑
（ 
，双灭锡），其反应步骤可写成：
（nBu＝正丁基，Cy＝环己基）
本发明是将1-环己基二丁基锡-1，2，4-三氮唑配制成20%的乳油，然后用水稀释1000～3000倍，对苹果树直接喷洒，对苹果上的山楂叶螨、全爪螨有较好的杀灭作用。
本发明是将1-环己基二丁基锡-1，2，4-三氮唑配制成20%的乳油，然后用水配制成有效成分5～100ppm的水溶液，对棉花立枯、小麦赤霉、水稻纹枯、芦笋茎枯、苹果轮纹、甜菜褐斑、芦笋褐斑、花生斑网等8种病原菌均有较好的抑菌效果。
实例1.
在含有450ml甲苯与50ml无水乙醚的混合溶剂反应瓶A中加入金属镁屑24.3克（1摩尔）。取氯代正丁烷92.54克（1摩尔）的五分之一加入反应瓶A中，其余与57.4克（0.22摩尔）四氯化锡及50ml甲苯合并后置于滴液漏斗B中。使A缓慢升温，反应引发后滴加上述混合液，滴毕保温回流三小时。反应毕降至20℃以下滴加5%盐酸250ml。滴毕静置分层，水层以50ml甲苯萃取，合并有机层，蒸去溶剂。减压蒸馏得四丁基锡为无色液体70.3克，沸点145℃/10mmHg收率92.09%。
实例2.
取实例1制备的四丁基锡69.4克（0.2摩尔）、四氯化锡52.2克（0.2摩尔）置于C反应瓶内，220℃反应三小时，减压蒸馏得白色固体二丁基二氯化锡112.4克，收率92.4%。
实例3.
将4.804克（0.28摩尔）金属镁屑加入到50ml四氯呋喃中，取33.18克（0.28摩尔）氯代环己烷制得环己基格氏试剂。将200ml甲苯置于反应瓶D中加入60.8克（0.2摩尔）实例2制备的二丁基二氯化锡，快速搅拌下滴加上述制得的格氏试剂，滴加温度控制在25℃以下，滴毕加热回流二小时后降至室温，20℃以下滴加5%盐酸70ml，滴毕静置分层，水层以50ml甲苯萃取，合并有机层蒸去溶剂后减压蒸馏得无色液体二丁基环己基氯化锡65.3克，沸点139-40℃/0.8-0.9mmHg，收率93%。
实例4.
取实例3制备出的二丁基环己基氯化锡140.4克（0.4摩尔）置于反应瓶E中，加入到180ml甲醇与45ml水的混合溶剂中，加入NaOH20克（0.5摩尔）加热回流2小时后冷却至室温。加入1000-1200ml水后用500-600ml乙醚分4-5次萃取，萃取液经蒸去溶剂得粘稠状乳白色液体，即氧化物。将氧化物移入含有400ml丙酮的反应瓶F中，加入1，2，4-三氮唑27.6克（0.4摩尔），加热搅拌回流6小时，静置过滤，滤饼用水洗涤，抽干，经干燥得白色固体产物1-环己基二丁基锡-1，2，4-三氮唑136.2克，收率88.7%，熔点：171-4℃。
实例5.
防治苹果上山楂 叶螨试验。
在辽宁农科院园艺所果园进行田间小区试验。20%双灭锡乳油分别以1000倍、2000倍、3000倍，对照药剂三氯杀螨醇1000倍，清水空白对照，每个浓度处理为6棵树，随机排列，三次重复。施药前每个处理调查6棵树，每棵树分东、南、西、北中五个方位，每个方位固定一枝各带有4张叶片，即每棵树调查20张叶片上的螨数，施药后2、7、15、30、40天调查固定叶片上的活螨数，用虫口减退率表示防效。
施药后虫口减退率＝ (施药前虫口数-施药后虫口数)/(施药前虫口数) ×100
结果见表一。
实例6.
防治苹果全爪螨试验。
在山东烟台农科所，20%双灭锡乳油分别以1000、2000倍，对照药剂三唑锡20%悬浮剂1500倍，另设空白对照。施药前调查每百叶上螨与卵的基数，施药后10天、20天、35天分别调查螨与卵的每百叶头数及矫正减退率。结果见表二。
实例7.
室内离体活性与多菌灵比较。
在南开大学元素所生测室室内进行。双灭锡配制成5、25、100ppm，MBC配制成25、50ppm，分别对棉花立枯、小麦赤霉、水稻纹枯、芦笋茎枯、苹果轮纹、甜菜褐斑、芦笋褐斑、花生斑网等8种病原菌进行抑菌试验，结果见表三。
Claims (2)
1、一种合成1-环己基二丁基锡-1，2，4三氮唑( ，双灭锡)，杀菌、杀螨剂的方法，它是用氯代正丁烷、四氯化锡和氯代环己烷为基本原料，经下列反应步骤：
(：Bu=正丁基，Cy=环己基)
其特征在于：
令金属镁屑与氯代正丁烷以甲苯和无水乙醚作混合溶剂在反应瓶A中缓慢升温引发反应，然后向其中滴加以甲苯作溶剂的氯代正丁烷和四氯化锡混合液，滴毕保温回流三小时，降温20℃以下滴加稀酸，分离出有机层，蒸去溶剂，减压蒸馏得四丁基锡；
令上述四丁基锡和四氯化锡在反应瓶C中220℃温度下反应三小时，减压蒸馏得二丁基二氯化锡；
将以四氢呋喃为溶剂金属镁屑和氯代环己烷反应制得的环己基格氏试剂快速搅拌25℃以下滴加入含甲苯为溶剂上述制备的二丁基二氯化锡反应瓶D中，滴毕加热回流二小时，降至20℃以下滴加稀酸，分离出有机层，蒸去溶剂，减压蒸馏得二丁基环己基氯化锡；
令上述二丁基环己基氯化锡以甲醇和水为混合溶剂在反应瓶E中与氢氧化钠反应，加热回流二小时，冷却至室温，加水稀释后用乙醚萃取，蒸出溶剂后得乳白色液体氧化物，然后将其移入反应瓶F中，以丙酮作溶剂与1，2，4-三氮唑一起加热回流6小时，静置、过滤，水洗后经干燥即得白色固体产物1-环己基二丁基锡-1，2，4-三氮唑。
2、按照权项1所说的合成方法，其特征在于所述氯代正丁烷与金属镁反应制成格氏试剂然后与四氯化锡反应的摩尔比为1∶1∶0.22;所述四丁基锡与四氯化锡反应的摩尔比为1∶1;所述二丁基二氯化锡与环己基格氏试剂反应的摩尔比为1∶1.4;所述二丁基环己基氯化锡碱解，再与1，2，4-三氮唑反应的摩尔比为1∶1.25∶1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91101933 CN1027894C (zh) | 1991-03-27 | 1991-03-27 | 1-环己基二丁基锡-1，2，4-三氮唑合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91101933 CN1027894C (zh) | 1991-03-27 | 1991-03-27 | 1-环己基二丁基锡-1，2，4-三氮唑合成方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065272A true CN1065272A (zh) | 1992-10-14 |
| CN1027894C CN1027894C (zh) | 1995-03-15 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91101933 Expired - Fee Related CN1027894C (zh) | 1991-03-27 | 1991-03-27 | 1-环己基二丁基锡-1，2，4-三氮唑合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027894C (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555257B (zh) * | 2009-05-18 | 2011-12-14 | 南开大学 | 1-芳基-3,5-二甲基吡唑-4-甲酸有机锡衍生物合成方法和用途 |
-
1991
- 1991-03-27 CN CN 91101933 patent/CN1027894C/zh not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555257B (zh) * | 2009-05-18 | 2011-12-14 | 南开大学 | 1-芳基-3,5-二甲基吡唑-4-甲酸有机锡衍生物合成方法和用途 |
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| Publication number | Publication date |
|---|---|
| CN1027894C (zh) | 1995-03-15 |
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