CN104557713A - 高纯度氟虫腈制备方法 - Google Patents
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- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 title abstract 6
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- 238000000034 method Methods 0.000 claims abstract description 7
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- 239000003638 chemical reducing agent Substances 0.000 claims abstract 2
- FNELVJVBIYMIMC-UHFFFAOYSA-N Ethiprole Chemical compound N1=C(C#N)C(S(=O)CC)=C(N)N1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl FNELVJVBIYMIMC-UHFFFAOYSA-N 0.000 claims description 28
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 3
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- 238000006193 diazotization reaction Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
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- ITNMAZSPBLRJLU-UHFFFAOYSA-N 2,6-dichloro-4-(trifluoromethyl)aniline Chemical compound NC1=C(Cl)C=C(C(F)(F)F)C=C1Cl ITNMAZSPBLRJLU-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- DBNLGTYGKCMLLR-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]hydrazine Chemical compound NNC1=CC=C(C(F)(F)F)C=C1 DBNLGTYGKCMLLR-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
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- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
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- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
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- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及的是高纯度98-99％含量的杀虫剂氟虫腈的制备方法，具体为采用先将低含量93-95％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑通过选取合适还原剂业制备含量高达99.8％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，再与98％三氟甲基亚硫酰氯反应制得含量可达98％-99％氟虫腈，从而解决了高纯度氟虫腈制备的难题，避免用低含量氟虫腈原药提纯而不易得到高含量氟虫腈的工艺路线，克服了现有制备技术存在的不足。本发明整个合成及提纯方法所采用原料易得，工艺条件简便，产物品质优。
Description
技术领域
本发明涉及的是氟虫腈的制备方法，具体为含量达98％-99％氟虫腈制备方法。
背景技术
吡唑环是生产氟虫腈、乙虫腈等高端农药品种所需的关键中间体。氟虫腈是由法国罗纳-普朗克公司首先开发的高效杀虫剂，氟虫腈化学名：5-氨基-3-氰基1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑，氟虫腈通过γ-氨基丁酸调节的氯通道干扰氯离子的通道，破坏正常中枢神经系统的活性并造成个体死亡。由于这种独特的作用，使氟虫腈具有不同于常规杀虫剂的显著特点。乙虫腈(Ethiprole)是由罗纳普朗克发现、拜耳公司开发的杀虫、杀螨剂，属于第二代作用于GABA的杀虫剂低用量下对多种咀嚼式和刺吸式害虫有效，可用于种子处理和叶面喷雾，持效期长达21-28d。(主要用于防治蓟马、蝽、象虫、甜菜麦蛾、蚜虫、飞虱和蝗虫等，对某些粉虱也表现出活性(特别是对极难防治的水稻害虫稻绿蝽有很强的活性)。
目前制备氟虫腈方法主要有三种路线：路线1是由5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑与三氟甲硫基卤代烷反应，引入三氟甲硫基，再经间氯过氧苯甲酸氧化而得到氟虫腈；路线2是由5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑先制备双硫代物，用卤代烷经三氟乙酸/过氧化氢氧化得到氟虫腈；路线3是由5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑与亚磺酰基取代物反应一步合成得到氟虫腈。
以上三种路线5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)(中文名：吡唑环)均作为制备必需的关键中间体。目前合成吡唑环的方法主要有两种路线：一是以2，6-二氯-4-三氟甲基苯胺为原料，以硫酸为反应介质，滴加亚硝酸钠的水溶液进行重氮化反应，重氮化反应液在一定温度下，加入2，3-二氰基丙酸乙酯，在弱碱性条件下于有机溶剂中进行环化反应，反应结束后经后处理得到95％含量的吡唑环。二是以4-三氟甲基苯肼为原料合成的方法，称为“肼路线”，合成可得93％含量的吡唑环。通过以上路线制得的吡唑环，直接与三氟甲基亚硫酰氯在溶剂甲苯、醋酸酐及催化剂的釜中，经一定条件反应得氟虫腈粗品，离心母液回收甲苯，得到的氟虫腈含量为88％-90％，经精制后得95％的氟虫腈。
发明内容
本发明的目的采用先制备含量达99.8％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，再与98％三氟甲基亚硫酰氯反应制得含量可达98％-99％氟虫腈，从而解决了高含量氟虫腈合成的难题，避免用低含量氟虫腈原药提纯而不易得到高含量氟虫腈的工艺路线，克服了现有制备技术存在的不足。
本发明的技术解决方案是：首先在氯化苯溶剂中加入93-95％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，同时加入还原剂，其还原剂成分选自次磷酸钠、水合肼中的一种，通过升温、搅拌、冷却、离心、烘干，得到含量达99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑；然后将含量达99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑再与98％三氟甲基亚硫酰氯、甲苯溶剂，在催化剂条件下反应制得98-99％含量的氟虫腈，具体反应方程式为：
含量达98-99％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的制备方法，具体步骤如下：
1、将工业品93-95％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，加入氯化苯溶剂中；
2、加入还原剂，还原剂成分选自次磷酸钠、水合肼中的一种，搅拌升温；
3、冷却、结晶、离心、烘干得99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑；
4、将CF3SOCl加入到合适反应试剂中，反应、升温，然后加入99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑及对甲苯磺酸二甲胺盐混合物，同时加入催化剂，反应10小时后，减压蒸去溶剂，得到98-99％氟虫腈原药。
Claims (3)
1.高纯度氟虫腈的制备方法，其特征在于：先制备含量达99.8％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，再与98％三氟甲基亚硫酰氯反应制得含量可达98％-99％氟虫腈。
合成及提纯方法包括步骤：首先在氯化苯溶剂中加入93-95％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，同时加入还原剂，其还原剂成分选自次磷酸钠、水合肼中的一种，通过升温、搅拌、冷却、离心、烘干，得到含量达99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑；然后将含量达99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑再与98％三氟甲基亚硫酰氯、甲苯溶剂，在催化剂条件下反应制得98-99％含量的氟虫腈，具体反应方程式为：
含量98-99％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的制备方法，具体步骤如下：先将工业品93-95％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑，加入氯化苯溶剂中；然后加入还原剂，还原剂成分选自次磷酸钠、水合肼中的一种，搅拌升温；冷却、结晶、离心、烘干得99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑；最后将CF3SOCl加入到合适反应试剂中，反应、升温，然后加入99.5％的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑及对甲苯磺酸二甲胺盐混合物，同时加入催化剂，反应10小时后，减压蒸去溶剂，得到98-99％氟虫腈原药。
2.根据权利要求1所述的高纯度氟虫腈制备方法，其特征在于：合适还原剂，还原剂成分选自次磷酸钠、水合肼中的一种。
3.根据权利要求1所述的高纯度氟虫腈制备方法，其特征在于：控制温度为10小时。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573509A (zh) * | 2022-03-28 | 2022-06-03 | 江苏托球农化股份有限公司 | 一种氟虫腈绿色生产工艺 |
| CN115353490A (zh) * | 2022-09-26 | 2022-11-18 | 安徽美诺华药物化学有限公司 | 一种氟虫腈的纯化工艺 |
| CN115594635A (zh) * | 2022-09-29 | 2023-01-13 | 浙江美诺华药物化学有限公司（Cn） | 一种去氯氟虫腈的合成方法 |
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| CN115353490A (zh) * | 2022-09-26 | 2022-11-18 | 安徽美诺华药物化学有限公司 | 一种氟虫腈的纯化工艺 |
| CN115594635A (zh) * | 2022-09-29 | 2023-01-13 | 浙江美诺华药物化学有限公司（Cn） | 一种去氯氟虫腈的合成方法 |
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