5-(difluoromethoxy)-1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazole | 656825-65-9

• 物质功能分类: 有机原料 - 杂环化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 5-(difluoromethoxy)-1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazole
• 英文别名: 5-(difluoromethoxy)-1,4-dimethyl-3-(trifluoromethyl)pyrazole
• CAS: 656825-65-9
• 化学式: C₇H₇F₅N₂O
• 分子量: 230.137
• InChiKey: AGXPLJDEOKTGGR-UHFFFAOYSA-N

物化性质

• 沸点：
  200.5±40.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  27
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5-(difluoromethoxy)-1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazole 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 反应 5.0h， 以89%的产率得到4-(bromomethyl)-5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl) 1H-pyrazole
  参考文献：
  名称：

  [EN] 1,3,4-THIADIAZOLES HAVING A HERBICIDAL ACTIVITY, THEIR AGRONOMICAL COMPOSITIONS AND RELATIVE USE
  [FR] 1,3,4-THIADIAZOLES PRÉSENTANT UNE ACTIVITÉ HERBICIDE, LEURS COMPOSITIONS AGRONOMIQUES ET UTILISATION ASSOCIÉE

  摘要：

  本发明涉及一种具有通式(I)的新噻二唑衍生物，以及它们作为除草剂的用途。

  公开号：

  WO2016042435A1
• 作为产物：
  描述：

  1,4-dimethyl-5-hydroxy-3-trifluoromethyl-1H-pyrazole 、 氟里昂-22 在 氢氧化钾 作用下， 以 异丙醇 为溶剂， 反应 2.0h， 以88.5%的产率得到5-(difluoromethoxy)-1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazole
  参考文献：
  名称：

  PYRAZOLE DERIVATIVES AND PROCESS FOR THE PRODUCTION THEREOF

  摘要：

  公开号：

  EP1541561B1

文献信息

• Herbicidally Active Composition
  申请人：Hupe Eike

  公开号：US20100190794A1

  公开（公告）日：2010-07-29

  The present invention relates to herbicidally active compositions comprising at least one piperazinedione compound of the formula I in which: R x , R y are each hydrogen or together are a chemical bond; R 1 is cyano or nitro; R 2 is hydrogen, fluorine, chlorine, C 1 -C 2 -alkyl, ethenyl or C 1 -C 2 -alkoxy; R 3 is fluorine or hydrogen; R 4 is methyl; R 5 is hydrogen, methyl or ethyl; R 6 is hydrogen, methyl or ethyl; and R 7 is hydrogen or halogen; and at least one further active compound selected from the group consisting of b1) lipid biosynthesis inhibitors; b2) acetolactate synthase inhibitors (ALS inhibitors); b3) photosynthesis inhibitors; b4) protoporphyrinogen-IX oxidase inhibitors, b5) bleacher herbicides; b6) enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP inhibitors); b7) glutamine synthetase inhibitors; b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors); b9) mitose inhibitors; b10) inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); b11) cellulose biosynthesis inhibitors; b12) decoupler herbicides; b13) auxin herbicides; b14) auxin transport inhibitors; b15) other herbicides, and C) safeners.

  本发明涉及具有至少一种式I的哌嗪二酮化合物的除草活性组合物： 其中： Rx，Ry分别为氢或一起为化学键； R1为氰基或硝基； R2为氢、氟、氯、C1-C2-烷基、乙烯基或C1-C2-烷氧基； R3为氟或氢； R4为甲基； R5为氢、甲基或乙基； R6为氢、甲基或乙基；以及 R7为氢或卤素； 以及从以下组中选择的至少一种进一步活性化合物： b1）脂质生物合成抑制剂； b2）乙酰乳酸合成酶抑制剂（ALS抑制剂）； b3）光合作用抑制剂； b4）原卟啉原生物合成酶抑制剂； b5）漂白剂除草剂； b6）烯丙基酮酸磷酸合酶抑制剂（EPSP抑制剂）； b7）谷氨酰胺合成酶抑制剂； b8）7,8-二氢叶酸合成酶抑制剂（DHP抑制剂）； b9）有丝分裂抑制剂； b10）非常长链脂肪酸合成抑制剂（VLCFA抑制剂）； b11）纤维素生物合成抑制剂； b12）解偶联剂除草剂； b13）生长素除草剂； b14）生长素转运抑制剂； b15）其他除草剂；以及 C）安全剂。
• [EN] PROCESS AND INTERMEDIATES FOR THE PREPARATION OF PYROXASULFONE, FENOXASULFONE AND VARIOUS SULFONE ANALOGS OF 5,5-DIMETHYL-4H-1,2-OXAZOLE<br/>[FR] PROCÉDÉ ET INTERMÉDIAIRES POUR LA PRÉPARATION DE PYROXASULFONE, DE FENOXASULFONE ET DE DIVERS ANALOGUES DE SULFONE DE 5,5-DIMÉTHYL-4H-1,2-OXAZOLE
  申请人：ADAMA AGAN LTD

  公开号：WO2022009044A1

  公开（公告）日：2022-01-13

  The invention relates to a process for preparing immediate precursors for pyroxasulfone and fenoxasulfone preparation of the formula (I). The process comprises a bromination reaction of a benzylic position without light irradiation (step a), followed by thoination reaction, which substitutes the bromine atom (step b) and after the protecting group is removed, and the revealed thiol or thiolate reacts with a substituted isoxazoline bearing a leaving group at the 3-position (step c), wherein Y = protecting group. In another variant of the invention the pyroxasulfone or fenoxasulfone immediate precursor is synthesized from the arylmethyl bromide by first forming a carbon-sulfur bond at the 3-position of a 2-isoxazoline through displacement of a leaving group at the 3-position (particularly acid derived residues such as phosphoryl, sulfanyl, halo, cyano or carboxyl groups) by an appropriate thionating reagent. The resulting adducts, which is a S-protected 3-thio-2-isoxazoline, may be treated with base to remove the protecting group, to reveal a thiol or thiolate which may subsequently react with the arylmethyl bromide to form the Pyroxasulfone or Fenoxasulfone immediate precursor. Ar = aryl, Y = protecting group and X = leaving group.

  本发明涉及一种制备式(I)中的吡罗砜和芬氧砜的直接前体的方法。该方法包括在没有光照射的情况下对苯基位置进行溴化反应（步骤a），然后进行硫酰化反应，以取代溴原子（步骤b），并在去除保护基后，暴露的巯基或巯酸盐与在3位带有离去基团的取代异噁唑啉发生反应（步骤c），其中Y = 保护基。在本发明的另一种变体中，通过首先通过适当的硫化试剂将碳硫键形成在2-异噁唑啉的3位上，以取代3位的离去基团（特别是酸衍生残基，如磷酰基，硫酰基，卤素，氰或羧基团），从而合成了吡罗砜或芬氧砜的直接前体。生成的产物是S-保护的3-硫代-2-异噁唑啉，可以用碱处理以去除保护基，暴露出巯基或巯酸盐，随后可以与苯基甲基溴反应，形成吡罗砜或芬氧砜的直接前体。Ar = 芳基，Y = 保护基，X = 离去基团。
• Pyrazole derivatives and process for the production thereof
  申请人：Nakatani Masao

  公开号：US20050215797A1

  公开（公告）日：2005-09-29

  The present invention provides pyrazole derivatives useful as production intermediates for isoxazoline derivatives having an excellent herbicidal effect and selectivity between crops and weeds as well as processes for producing the same. The pyrazole derivatives or pharmaceutically acceptable salts thereof which are inventive compounds are represented by the general formula [I] or a salt thereof: wherein R 1 represents a C1 to C6 alkyl group, R 2 represents a C1 to C3 haloalkyl group, R 3 represents a hydrogen atom, a C1 to C3 alkyl group which may be substituted with one or more substituents selected from the following substituent group α, or a formyl group, R 4 represents a hydrogen atom or a C1 to C3 haloalkyl group, provided that R 4 represents a C1 to C3 haloalkyl group in the case that R 3 is a hydrogen or a formyl group, and R 4 is a hydrogen group or a C1 to C3 haloalkyl group in the case that R 3 is a C1 to C3 alkyl group which may be substituted with one or more substituents selected from the following substituent group α.

  本发明提供了吡唑衍生物，用作制备具有优异除草效果和作物与杂草之间选择性的异恶唑衍生物的生产中间体，以及制备它们的方法。发明化合物为吡唑衍生物或其药学上可接受的盐，其由通式[I]或其盐表示：其中，R1代表C1至C6烷基，R2代表C1至C3卤代烷基，R3代表氢原子，C1至C3烷基，其可以被以下取代基α中的一个或多个取代基取代，或者甲酰基，R4代表氢原子或C1至C3卤代烷基，前提是当R3为氢或甲酰基时，R4代表C1至C3卤代烷基，在R3为C1至C3烷基且可以被以下取代基α中的一个或多个取代基取代时，R4代表氢原子或C1至C3卤代烷基。
• PROCESS AND INTERMEDIATES FOR THE PREPARATION OF PYROXASULFONE, FENOXASULFONE AND VARIOUS SULFONE ANALOGS OF 5,5-DIMETHYL-4H-1,2-OXAZOLE
  申请人：Adama Agan Ltd.

  公开号：EP3936503A1

  公开（公告）日：2022-01-12

  The invention relates to a process for preparing immediate precursors for pyroxasulfone and fenoxasulfone preparation of the formula (I). The process comprises a bromination reaction of a benzylic position without light irradiation (step a), followed by thoination reaction, which substitutes the bromine atom (step b) and after the protecting group is removed, and the revealed thiol or thiolate reacts with a substituted isoxazoline bearing a leaving group at the 3-position (step c). wherein Y = protecting group In another variant of the invention the pyroxasulfone or fenoxasulfone immediate precursor is synthesized from the arylmethyl bromide by first forming a carbon-sulfur bond at the 3-position of a 2-isoxazoline through displacement of a leaving group at the 3-position (particularly acid derived residues such as phosphoryl, sulfanyl, halo, cyano or carboxyl groups) by an appropriate thionating reagent. The resulting adducts, which is a S-protected 3-thio-2-isoxazoline, may be treated with base to remove the protecting group, to reveal a thiol or thiolate which may subsequently react with the arylmethyl bromide to form the Pyroxasulfone or Fenoxasulfone immediate precursor. Ar = aryl, Y = protecting group and X = leaving group

  本发明涉及一种制备式（I）吡唑砜和唑醚砜直接前体的工艺。该工艺包括在没有光照射的情况下对苄基位置进行溴化反应（步骤 a），然后进行硫化反应，取代溴原子（步骤 b），在去掉保护基后，显露出来的硫醇或硫酸盐与在 3 位上带有离去基团的取代异噁唑啉反应（步骤 c）。 其中 Y = 保护基团 在本发明的另一个变体中，首先通过适当的亚硫酸化试剂置换 2-异噁唑啉 3 位上的离去基团（特别是酸衍生残基，如磷酰、硫酰、卤代、氰基或羧基），在 3 位上形成碳-硫键，从而从芳基甲基溴合成吡唑砜或芬禾砜直接前体。生成的加合物是受 S 保护的 3-硫代-2-异噁唑啉，可用碱处理以去除保护基团，从而显示出硫醇或硫代酸酯，随后可与芳基甲基溴反应生成吡唑砜或唑醚砜直接前体。 Ar = 芳基，Y = 保护基，X = 离去基团
• 一种砜吡草唑中间体的制备方法
  申请人：绍兴贝斯美化工股份有限公司

  公开号：CN114716379A

  公开（公告）日：2022-07-08

  本发明公开了一种制备砜吡草唑中间体4‑(卤代甲基)‑5‑(二氟甲氧基)‑1‑甲基‑3‑(三氟甲基)‑1H‑吡唑的制备方法，包括以化合物SCF‑3为原料以及反应溶剂，SCF‑3与卤代试剂在引发剂的作用下反应得到以SCF‑4为溶质的SCF‑3溶液；将以SCF‑4为溶质的SCF‑3溶液与硫脲反应得到SCF‑5；回收所述SCF‑5中的SCF‑3反应溶剂，然后加入洗涤溶剂，打浆搅拌，室温下抽滤得到滤饼，对所述滤饼进行干燥得到固体SCF‑5；将滤液经蒸馏回收洗涤溶剂和SCF‑3。该方法能够避免四氯化碳的产生，并产生较少的二卤代副产物，原料利用率较高。