CN103387541B - 一种取代吡唑醚类化合物的制备方法 - Google Patents
一种取代吡唑醚类化合物的制备方法 Download PDFInfo
- Publication number
- CN103387541B CN103387541B CN201210144760.0A CN201210144760A CN103387541B CN 103387541 B CN103387541 B CN 103387541B CN 201210144760 A CN201210144760 A CN 201210144760A CN 103387541 B CN103387541 B CN 103387541B
- Authority
- CN
- China
- Prior art keywords
- compound
- preparation
- per
- weight
- solvent
- 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.)
- Active
Links
- 0 *[n]1nccc1-c1ccccc1 Chemical compound *[n]1nccc1-c1ccccc1 0.000 description 7
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明属于有机合成领域，提供了一种取代吡唑醚类化合物的制备方法：包括先将化合物II制备成相应的金属盐，然后在助溶剂作用下与化合物III反应得到化合物I的粗品，经结晶制得高纯度的化合物I。反应式如下：
Description
技术领域
本发明属于有机合成领域，具体涉及一种取代吡唑醚类化合物的制备方法。
背景技术
杀菌剂唑菌酯（pyraoxystrobin，CN1657524）具有高效、广谱的杀菌活性，在该化合物的研究过程中发现如下通式化合物也具有很好的杀菌活性：
专利WO9933812中虽提到了多条路线制备该类化合物，但均使用常规合成方法，反应时间长，过程繁琐，且目标产物是通过柱层析提纯得到的，收率不足50%。由于反应过程中极容易产生N-烷基化异构体副产物且提纯困难，用已知的其他方法也不能很好的解决此问题，因而难以实现规模化生产。
发明内容
为了满足工业化生产的需要，本发明致力于开发一种收率和纯度较高、且成本又较低的制备结构式I的方法。发明人经过详尽的研究，提出了本发明所用的方法以解决现有技术中存在的“易产生副产N-烷基化异构体、提纯困难”的难题。
本发明的技术方案如下：
一种如式（I）所示的取代吡唑醚类化合物的制备方法，反应式如下：
式中：R1选自CH3或Cl；n=0-2；R2选自H或CH3；R3选自CH3；X选自Cl或Br；Q选自Q1、Q2、Q3或Q4：
在制备过程中首先将化合物II成盐、即采用成盐法制备目的产物，可以大大提高目的产物的收率和选择性。
上述制备方法得到的产物中仅含有的少量副产化合物IV，采用重结晶方法进行精制，可以得到高纯度的目标化合物I。
本发明的具体方案如下：
1、化合物II首先于有机溶剂中制备成金属盐，然后加入助溶剂和化合物III反应得到化合物I粗品，反应温度50-120℃；
2、将化合物I粗品于1-20倍重量的醇或醇的水溶液中重结晶，得到目标化合物I。
本发明所采用的原料化合物II可以参考文献JournalofHeterocyclicChemistry(1972),95(6),1219-25中报道的方法制备，化合物III参考专利US4723034、US5554578和US5824705合成。
制备化合物II的金属盐所用的有机溶剂选自高沸点惰性非极性溶剂，溶剂的用量为化合物II重量的3-50倍；优选甲苯、二甲苯、苯、正己烷、环己烷或石油醚中的一种或其混合溶剂，用量为化合物II重量的5-20倍。
制备化合物II的金属盐时，化合物II与碱的适宜加料比以摩尔计为1：0.9-1。适宜的碱选自氢氧化钠、氢氧化钾、金属钠、氢化钠、氨基钠、叔丁醇钠（或钾）、甲（或乙）醇钠（或钾）、碳酸钠或碳酸钾。当采用金属钠、氢化钠、氨基钠、叔丁醇钠（或钾）、甲（或乙）醇钠（或钾）制备化合物II的金属盐时，可以利用上述高沸点非极性溶剂，在高温下产生的气体自然逸出或者通过负压带出，或者产生的醇通过蒸馏方法分出后，得到化合物II的金属盐。进一步优选的碱为氢氧化钠、氢氧化钾、氢化钠、氨基钠、甲醇钠或碳酸钾。然而更为经济方便的方法是将化合物II与氢氧化钠（或钾）水溶液在高沸点非极性惰性溶剂中回流分水制得其金属盐，优选采用30-50%氢氧化钠（或钾）水溶液。
化合物II的金属盐制备完毕，加入助溶剂和化合物III，继续保温反应制备化合物I；其中化合物II与化合物III的投料摩尔比为1-1.05：1；所述的助溶剂选自N，N-二甲基甲酰胺、二甲亚砜或N-甲基吡咯烷酮等，助溶剂的加入量与高沸点惰性非极性溶剂的重量比为0.05-1：1。
制备化合物II的金属盐和化合物I的反应温度优选80-115℃。
研究发现，反应时加入适量的PEG（聚乙二醇）系列催化剂有利于有机盐在反应体系中的分布，提高反应速度。所述的催化剂优选PEG-200，PEG-400或PEG-600，催化剂加入量为原料化合物II重量的0.1%-10%，优选0.5%-5%。
当化合物III中X选自氯时，加入催化量的碘化钾（或钠）更有利于反应的进行。
反应终点通过高效液相色谱跟踪至原料化合物II反应完毕。反应完成后，加水分出助溶剂，常压或减压蒸出反应溶剂循环套用于下批反应，得到化合物I粗品。
产品含量以高效液相色谱采用外标法测定。
为了获得高品质的目的产物，本发明提供了一种简易高效的重结晶方法。发明人将上述制备方法得到的化合物I粗品在醇或醇的水溶液中重结晶提纯，所述的醇选自甲醇、乙醇、异丙醇等或其水溶液，优选异丙醇的水溶液；溶剂使用量为化合物I的理论重量的1-20倍，优选3-10倍，其中水的使用量为化合物I的理论重量的0-10倍，优选1-5倍。较为合适的结晶温度为-10-50℃，优选5-30℃；结晶时间通常为2-48小时，优选10-24小时。
化合物I的结晶过程中可以不加入晶种进行结晶。但若没有晶种存在，可能导致结晶时间较长，且产品晶型不规则，产品含量略低。因此优选在结晶过程中加入适量晶种，这样可以大大加快结晶速度，改善产品晶型，提高产品含量。结晶过程中晶种加入量一般为化合物I理论重量的0.01-2%，优选0.05-1%。
重结晶母液套用3-5次后，可以通过蒸馏的方式回收，然后通过加入醇或者水调节至合适的比例后，继续使用。
采用本发明的方法制备的部分式（I）所示的取代吡唑醚类化合物列举于表1，但本发明的制备方法并不限于仅制备表1中的化合物。
表1
| 编号 | (R1)n | R2 | R3 | Q |
| 1 | - | H | CH3 | Q1 |
| 2 | 4-Cl | H | CH3 | Q1 |
| 3 | 4-CH3 | H | CH3 | Q1 |
| 4 | - | CH3 | CH3 | Q1 |
| 5 | 4-Cl | CH3 | CH3 | Q1 |
| 6 | 4-CH3 | CH3 | CH3 | Q1 |
| 7 | - | H | CH3 | Q2 |
| 8 | 4-Cl | H | CH3 | Q2 |
| 9 | 4-CH3 | H | CH3 | Q2 |
| 10 | - | CH3 | CH3 | Q2 |
| 11 | 4-Cl | CH3 | CH3 | Q2 |
| 12 | 4-CH3 | CH3 | CH3 | Q2 |
| 13 | - | CH3 | CH3 | Q3 |
| 14 | 4-Cl | CH3 | CH3 | Q3 |
| 15 | 4-CH3 | CH3 | CH3 | Q3 |
| 16 | - | H | CH3 | Q4 |
| 17 | 4-Cl | H | CH3 | Q4 |
| 18 | 4-CH3 | H | CH3 | Q4 |
| 19 | - | CH3 | CH3 | Q4 |
| 20 | 4-Cl | CH3 | CH3 | Q4 |
| 21 | 4-CH3 | CH3 | CH3 | Q4 |
“-”表示苯环上无取代基
本发明的制备方法具有以下优点：操作简单、三废量少；产品收率高，一般可达85%以上，优选条件下可达到95%；产品质量好，各批产品含量均可达到95%以上。
具体实施方式
以下具体实施例用来进一步说明本发明，但本发明绝非仅限于这些例子。
实施例1化合物19的制备
先将化合物1,4-二甲基-5-苯基-1H-吡唑-3-醇（II-1）19.0g（0.1mol，含量99%）、甲苯100g加入到反应体系中，氮气保护下搅拌下加入含量50%氢氧化钠水溶液8.3g（0.1mol），升温至回流，待分出水达到理论量时成盐反应完成，加入N，N-二甲基甲酰胺10g，然后滴加2-(溴甲基)苯基(甲氧基)氨基甲酸甲酯（III-1）（参考专利US5824705合成）36.5g（0.1mol，含量75%），保温100℃反应2h，反应完成。反应液降至室温，向其中加入50g的水，分层，有机层用50g水洗一次，减压脱溶后得到目标化合物粗品46.0g，HPLC归一含量约82.6%。
向该粗品中加入异丙醇186.4g，搅拌升温至45℃，保温加水80g，约在1小时内降温至20-25℃，加入0.3g晶种，保温结晶约15小时，然后降温至4℃，继续搅拌2小时，过滤，干燥得到产品36.1g，熔点66-68℃，含量96.9%，收率91.8%。
实施例2化合物19的制备
合成过程同实施例1。
向该粗品中加入异丙醇150g，升温至60℃，然后加入水80g，约在1小时内降温至20-25℃，保温结晶约15小时，开始有晶体析出，继续搅拌约20小时，然后降温至4℃，继续搅拌2小时，过滤，干燥得到产品34.2g，含量95.1%，收率85.4%。
实施例3化合物19的制备
先将化合物II-119.0g（0.1mol，99%）、甲苯100g和0.5gPEG-600加入到反应体系中，通氮气保护，搅拌加热升温至50℃，开始滴加0.1mol的50%氢氧化钾溶液，滴加完毕继续升温回流分水至分出水达到理论量，加入二甲基亚砜10g，然后滴加2-(溴甲基)苯基(甲氧基)氨基甲酸甲酯（III-1）36.5g（0.1mol，含量75%），保温100℃反应2h，反应完成。后处理方法同实施例1，得到目标化合物粗品46.6g，HPLC归一含量约85.6%。
向该粗品中加入乙醇186.4g，搅拌升温至45℃，保温加水70g，约在1小时内降温至20-25℃，加入0.3g晶种，保温结晶约15小时，然后降温至0℃，继续搅拌2小时，过滤，干燥得到产品37.2g，含量98.2%，收率95.9%。
实施例4化合物2的制备
制备与结晶方法同实施例1。
以(E)-2-(2-(氯甲基)苯基)-3-甲氧基丙烯酸甲酯（III-2）与5-(4-氯苯基)-1-甲基-1H-吡唑-3-醇（II-2）为原料得到目标化合物，熔点102-104℃，含量96.6%，收率90.9%。
实施例5化合物5的制备
制备与结晶方法同实施例1。
以(E)-2-(2-(氯甲基)苯基)-3-甲氧基丙烯酸甲酯（III-2）与5-(4-氯苯基)-1,4-二甲基-1H-吡唑-3-醇（II-3）为原料得到目标化合物，熔点69-72℃，含量96.5%，收率89.6%。
实施例6化合物10的制备
制备与结晶方法同实施例1。
以(E)-2-(2-溴甲基苯基)-2-甲氧亚氨基乙酸甲酯（III-3）与化合物II-1为原料得到目标化合物，含量95.5%，收率87.2%。
按照以上方法制备的部分化合物的核磁数据见表2。
表2
Claims (7)
1.一种取代吡唑醚类化合物的制备方法，反应式如下：
其中R1选自CH3或Cl；n＝0-2；R2选自H或CH3；R3选自CH3；X选自Cl或Br；Q选自Q1、Q2、Q3或Q4：
其特征在于按以下步骤操作：
1)化合物II首先于有机溶剂中制备成金属盐，然后加入助溶剂和化合物III，于50-120℃温度下反应得到化合物I粗品；
2)将化合物I粗品于1-20倍重量的醇或醇的水溶液中重结晶，得到目标化合物I；
所述的有机溶剂选自高沸点惰性非极性溶剂，溶剂的用量为化合物II重量的3-50倍；
制备化合物II的金属盐所用的碱选自氢氧化钠、氢氧化钾、氢化钠、氨基钠、甲醇钠或碳酸钾；化合物II与碱的投料摩尔比为1：0.9-1；
所述的助溶剂选自N,N-二甲基甲酰胺、二甲亚砜或N-甲基吡咯烷酮；助溶剂的加入量与高沸点惰性非极性溶剂的重量比为0.05-1：1。
2.按照权利要求1所述的制备方法，其特征在于：所述的有机溶剂选自甲苯、二甲苯、苯、正己烷、环己烷或石油醚中的一种或其混合溶剂，用量为化合物II重量的5-20倍。
3.按照权利要求1所述的制备方法，其特征在于：化合物II与化合物III的加料摩尔比为1-1.05：1。
4.按照权利要求1所述的制备方法，其特征在于：反应温度为80-115℃。
5.按照权利要求1所述的制备方法，其特征在于：制备化合物I的反应中加入PEG-200、PEG-400或PEG-600作为催化剂，催化剂加入量为原料化合物II重量的0.1％-10％。
6.按照权利要求1所述的制备方法，其特征在于：结晶所用的醇溶剂选自甲醇、乙醇、异丙醇，溶剂使用量为化合物I的理论重量的1-20倍，其中水的使用量为化合物I的理论重量的0-10倍；结晶温度为-10-50℃；结晶时间为2-48小时。
7.按照权利要求6所述的制备方法，其特征在于：结晶过程中加入化合物I重量0.01-2％的晶种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210144760.0A CN103387541B (zh) | 2012-05-10 | 2012-05-10 | 一种取代吡唑醚类化合物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210144760.0A CN103387541B (zh) | 2012-05-10 | 2012-05-10 | 一种取代吡唑醚类化合物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103387541A CN103387541A (zh) | 2013-11-13 |
| CN103387541B true CN103387541B (zh) | 2016-02-10 |
Family
ID=49531973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210144760.0A Active CN103387541B (zh) | 2012-05-10 | 2012-05-10 | 一种取代吡唑醚类化合物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103387541B (zh) |
Families Citing this family (151)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103563947B (zh) * | 2013-11-19 | 2015-08-19 | 中国中化股份有限公司 | 一种杀真菌组合物及其应用 |
| CN103563946B (zh) * | 2013-11-19 | 2016-02-10 | 沈阳中化农药化工研发有限公司 | 杀真菌组合物及其应用 |
| CN104336036B (zh) * | 2014-10-14 | 2017-04-12 | 沈阳中化农药化工研发有限公司 | 一种杀真菌组合物及其应用 |
| WO2016174042A1 (en) | 2015-04-27 | 2016-11-03 | BASF Agro B.V. | Pesticidal compositions |
| EP3371177A1 (en) | 2015-11-02 | 2018-09-12 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| BR112018008288A2 (pt) | 2015-11-04 | 2018-10-30 | Basf Se | uso de compostos de fórmula, compostos de fórmula, mistura, composição agroquímica e método para combater fungos |
| WO2017081312A1 (en) | 2015-11-13 | 2017-05-18 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| EP3373732A1 (en) | 2015-11-13 | 2018-09-19 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| WO2017085100A1 (en) | 2015-11-19 | 2017-05-26 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| CA3003946A1 (en) | 2015-11-19 | 2017-05-26 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| US20190098899A1 (en) | 2016-03-10 | 2019-04-04 | Basf Se | Fungicidal mixtures iii comprising strobilurin-type fungicides |
| BR112018069897B1 (pt) | 2016-04-11 | 2023-01-17 | Basf Se | Composto de fórmula i, composição agroquímica, processo para a preparação de compostos de fórmula i, uso não terapêutico de compostos e método para o combate de fungos fitopatogênicos nocivos |
| WO2018050421A1 (en) | 2016-09-13 | 2018-03-22 | Basf Se | Fungicidal mixtures i comprising quinoline fungicides |
| WO2018054723A1 (en) | 2016-09-26 | 2018-03-29 | Basf Se | Pyridine compounds for controlling phytopathogenic harmful fungi |
| WO2018054711A1 (en) | 2016-09-26 | 2018-03-29 | Basf Se | Pyridine compounds for controlling phytopathogenic harmful fungi |
| WO2018054721A1 (en) | 2016-09-26 | 2018-03-29 | Basf Se | Pyridine compounds for controlling phytopathogenic harmful fungi |
| WO2018065182A1 (en) | 2016-10-04 | 2018-04-12 | Basf Se | Reduced quinoline compounds as antifuni agents |
| WO2018073110A1 (en) | 2016-10-20 | 2018-04-26 | Basf Se | Quinoline compounds as fungicides |
| EP3555056A1 (en) | 2016-12-19 | 2019-10-23 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| EP3339297A1 (en) | 2016-12-20 | 2018-06-27 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| EP3338552A1 (en) | 2016-12-21 | 2018-06-27 | Basf Se | Use of a tetrazolinone fungicide on transgenic plants |
| EP3571190A1 (en) | 2017-01-23 | 2019-11-27 | Basf Se | Fungicidal pyridine compounds |
| WO2018149754A1 (en) | 2017-02-16 | 2018-08-23 | Basf Se | Pyridine compounds |
| BR112019015338B1 (pt) | 2017-02-21 | 2023-03-14 | Basf Se | Compostos de fórmula i, composição agroquímica, semente revestida, uso dos compostos e método para combater fungos nocivos fitopatogênicos |
| AU2018241628B2 (en) | 2017-03-31 | 2022-03-17 | Basf Se | Pyrimidinium compounds and their mixtures for combating animal pests |
| US20200187500A1 (en) | 2017-04-06 | 2020-06-18 | Basf Se | Pyridine compounds |
| US20200045974A1 (en) | 2017-04-07 | 2020-02-13 | Basf Se | Substituted Oxadiazoles for Combating Phytopathogenic Fungi |
| WO2018188962A1 (en) | 2017-04-11 | 2018-10-18 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| TW201838965A (zh) | 2017-04-20 | 2018-11-01 | 印度商Ｐｉ工業公司 | 新穎的苯胺化合物 |
| US20210084902A1 (en) | 2017-05-02 | 2021-03-25 | Basf Se | Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles |
| WO2018202491A1 (en) | 2017-05-04 | 2018-11-08 | Basf Se | Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi |
| CN110621669A (zh) | 2017-05-04 | 2019-12-27 | 巴斯夫欧洲公司 | 防除植物病原性真菌的取代5-卤代烷基-5-羟基异噁唑类 |
| BR112019022206A2 (pt) | 2017-05-05 | 2020-05-12 | Basf Se | Misturas fungicidas, composição agroquímica, uso da mistura, métodos para controlar fungos nocivos fitopatogênicos e para a proteção de material de propagação de plantas e material de propagação vegetal |
| WO2018210659A1 (en) | 2017-05-15 | 2018-11-22 | Basf Se | Heteroaryl compounds as agrochemical fungicides |
| WO2018210658A1 (en) | 2017-05-15 | 2018-11-22 | Basf Se | Heteroaryl compounds as agrochemical fungicides |
| WO2018210661A1 (en) | 2017-05-15 | 2018-11-22 | Basf Se | Heteroaryl compounds as agrochemical fungicides |
| WO2018210660A1 (en) | 2017-05-15 | 2018-11-22 | Basf Se | Heteroaryl compounds as agrochemical fungicides |
| EP3630731B1 (en) | 2017-05-30 | 2023-08-09 | Basf Se | Pyridine and pyrazine compounds for combating phytopathogenic fungi |
| WO2018219797A1 (en) | 2017-06-02 | 2018-12-06 | Basf Se | Substituted oxadiazoles for combating phytopathogenic fungi |
| US20200190043A1 (en) | 2017-06-19 | 2020-06-18 | Basf Se | 2-[[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryloxy](thio)acetamides for combating phytopathogenic fungi |
| WO2019002158A1 (en) | 2017-06-30 | 2019-01-03 | Basf Se | SUBSTITUTED TRIFLUOROMETHYLOXADIAZOLES FOR THE CONTROL OF PHYTOPATHOGENIC FUNGI |
| WO2019007719A1 (en) | 2017-07-07 | 2019-01-10 | Basf Se | PESTICIDE MIXTURES |
| WO2019025250A1 (en) | 2017-08-04 | 2019-02-07 | Basf Se | SUBSTITUTED TRIFLUOROMETHYLOXADIAZOLES FOR COMBATING PHYTOPATHOGENIC FUNGI |
| WO2019038042A1 (en) | 2017-08-21 | 2019-02-28 | Basf Se | SUBSTITUTED TRIFLUOROMETHYLOXADIAZOLES FOR THE CONTROL OF PHYTOPATHOGENIC FUNGI |
| EP3915379A1 (en) | 2017-08-29 | 2021-12-01 | Basf Se | Pesticidal mixtures |
| WO2019042932A1 (en) | 2017-08-31 | 2019-03-07 | Basf Se | METHOD FOR CONTROLLING RICE PARASITES IN RICE |
| EP3453706A1 (en) | 2017-09-08 | 2019-03-13 | Basf Se | Pesticidal imidazole compounds |
| US11076596B2 (en) | 2017-09-18 | 2021-08-03 | Basf Se | Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi |
| WO2019057660A1 (en) | 2017-09-25 | 2019-03-28 | Basf Se | INDOLE AND AZAINDOLE COMPOUNDS HAVING 6-CHANNEL SUBSTITUTED ARYL AND HETEROARYL CYCLES AS AGROCHEMICAL FUNGICIDES |
| BR112020006037A2 (pt) | 2017-10-13 | 2020-10-06 | Basf Se | compostos, misturas pesticidas, composição agroquímica, métodos para controlar pragas de invertebrados, para proteger plantas e para proteção de material de propagação de plantas, semente e uso de compostos de fórmula (i) |
| EP3713936B1 (en) | 2017-11-23 | 2021-10-20 | Basf Se | Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi |
| WO2019115511A1 (en) | 2017-12-14 | 2019-06-20 | Basf Se | Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles |
| CA3084405A1 (en) | 2017-12-15 | 2019-06-20 | Basf Se | Fungicidal mixture comprising substituted pyridines |
| EP3728204A1 (en) | 2017-12-20 | 2020-10-28 | PI Industries Ltd. | Fluoralkenyl compounds, process for preparation and use thereof |
| WO2019121143A1 (en) | 2017-12-20 | 2019-06-27 | Basf Se | Substituted cyclopropyl derivatives |
| BR112020012706A2 (pt) | 2018-01-09 | 2020-11-24 | Basf Se | uso de um composto de silietinil hetarila, composição para uso na redução de nitrificação, mistura agroquímica, métodos para reduzir a nitrificação e para tratamento de um fertilizante ou de uma composição |
| WO2019137995A1 (en) | 2018-01-11 | 2019-07-18 | Basf Se | Novel pyridazine compounds for controlling invertebrate pests |
| WO2019150311A1 (en) | 2018-02-02 | 2019-08-08 | Pi Industries Ltd. | 1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms |
| WO2019154665A1 (en) | 2018-02-07 | 2019-08-15 | Basf Se | New pyridine carboxamides |
| US20200354321A1 (en) | 2018-02-07 | 2020-11-12 | Basf Se | New pyridine carboxamides |
| EP3530118A1 (en) | 2018-02-26 | 2019-08-28 | Basf Se | Fungicidal mixtures |
| EP3530116A1 (en) | 2018-02-27 | 2019-08-28 | Basf Se | Fungicidal mixtures comprising xemium |
| WO2019166252A1 (en) | 2018-02-28 | 2019-09-06 | Basf Se | Fungicidal mixtures comprising fenpropidin |
| IL276745B2 (en) | 2018-02-28 | 2023-10-01 | Basf Se | Use of N-functional alkoxy pyrazole compounds as nitrification inhibitors |
| EP3758491A1 (en) | 2018-02-28 | 2021-01-06 | Basf Se | Use of pyrazole propargyl ethers as nitrification inhibitors |
| WO2019166561A1 (en) | 2018-02-28 | 2019-09-06 | Basf Se | Use of alkoxypyrazoles as nitrification inhibitors |
| WO2019166257A1 (en) | 2018-03-01 | 2019-09-06 | BASF Agro B.V. | Fungicidal compositions of mefentrifluconazole |
| EP3533331A1 (en) | 2018-03-02 | 2019-09-04 | Basf Se | Fungicidal mixtures comprising pydiflumetofen |
| EP3533333A1 (en) | 2018-03-02 | 2019-09-04 | Basf Se | Fungicidal mixtures comprising pydiflumetofen |
| EP3536150A1 (en) | 2018-03-06 | 2019-09-11 | Basf Se | Fungicidal mixtures comprising fluxapyroxad |
| WO2019175712A1 (en) | 2018-03-14 | 2019-09-19 | Basf Corporation | New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways |
| WO2019175713A1 (en) | 2018-03-14 | 2019-09-19 | Basf Corporation | New catechol molecules and their use as inhibitors to p450 related metabolic pathways |
| WO2019219464A1 (en) | 2018-05-15 | 2019-11-21 | Basf Se | Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi |
| WO2019219529A1 (en) | 2018-05-15 | 2019-11-21 | Basf Se | Mixtures comprising benzpyrimoxan and oxazosulfyl and uses and methods of applying them |
| WO2019224092A1 (en) | 2018-05-22 | 2019-11-28 | Basf Se | Pesticidally active c15-derivatives of ginkgolides |
| WO2020002472A1 (en) | 2018-06-28 | 2020-01-02 | Basf Se | Use of alkynylthiophenes as nitrification inhibitors |
| WO2020020777A1 (en) | 2018-07-23 | 2020-01-30 | Basf Se | Use of substituted 2-thiazolines as nitrification inhibitors |
| ES2969872T3 (es) | 2018-07-23 | 2024-05-23 | Basf Se | Uso de un compuesto de tiazolidina sustituida como inhibidor de la nitrificación |
| TW202009235A (zh) | 2018-08-17 | 2020-03-01 | 印度商皮埃企業有限公司 | 1,2-二硫醇酮化合物及其用途 |
| EP3613736A1 (en) | 2018-08-22 | 2020-02-26 | Basf Se | Substituted glutarimide derivatives |
| EP3628157A1 (en) | 2018-09-28 | 2020-04-01 | Basf Se | Method of controlling insecticide resistant insects and virus transmission to plants |
| EP3628156A1 (en) | 2018-09-28 | 2020-04-01 | Basf Se | Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants |
| CA3112042A1 (en) | 2018-09-28 | 2020-04-02 | Basf Se | Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof |
| EP3628158A1 (en) | 2018-09-28 | 2020-04-01 | Basf Se | Pesticidal mixture comprising a mesoionic compound and a biopesticide |
| EP3643705A1 (en) | 2018-10-24 | 2020-04-29 | Basf Se | Pesticidal compounds |
| WO2020095161A1 (en) | 2018-11-05 | 2020-05-14 | Pi Industries Ltd. | Nitrone compounds and use thereof |
| EP3670501A1 (en) | 2018-12-17 | 2020-06-24 | Basf Se | Substituted [1,2,4]triazole compounds as fungicides |
| EP3696177A1 (en) | 2019-02-12 | 2020-08-19 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP3730489A1 (en) | 2019-04-25 | 2020-10-28 | Basf Se | Heteroaryl compounds as agrochemical fungicides |
| WO2020239517A1 (en) | 2019-05-29 | 2020-12-03 | Basf Se | Mesoionic imidazolium compounds and derivatives for combating animal pests |
| EP3769623A1 (en) | 2019-07-22 | 2021-01-27 | Basf Se | Mesoionic imidazolium compounds and derivatives for combating animal pests |
| WO2020244970A1 (en) | 2019-06-06 | 2020-12-10 | Basf Se | New carbocyclic pyridine carboxamides |
| WO2020244969A1 (en) | 2019-06-06 | 2020-12-10 | Basf Se | Pyridine derivatives and their use as fungicides |
| BR112021021028A2 (pt) | 2019-06-06 | 2021-12-14 | Basf Se | Uso dos compostos de fórmula i, compostos da fórmula i, composição e método para combater fungos fitopatogênicos |
| EP3766879A1 (en) | 2019-07-19 | 2021-01-20 | Basf Se | Pesticidal pyrazole derivatives |
| WO2021063735A1 (en) | 2019-10-02 | 2021-04-08 | Basf Se | New bicyclic pyridine derivatives |
| WO2021063736A1 (en) | 2019-10-02 | 2021-04-08 | Basf Se | Bicyclic pyridine derivatives |
| CA3162521A1 (en) | 2019-12-23 | 2021-07-01 | Basf Se | Enzyme enhanced root uptake of agrochemical active compound |
| US20230106291A1 (en) | 2020-02-28 | 2023-04-06 | BASF Agro B.V. | Methods and uses of a mixture comprising alpha-cypermethrin and dinotefuran for controlling invertebrate pests in t |
| WO2021175669A1 (en) | 2020-03-04 | 2021-09-10 | Basf Se | Use of substituted 1,2,4-oxadiazoles for combating phytopathogenic fungi |
| BR112022020612A2 (pt) | 2020-04-14 | 2022-11-29 | Basf Se | Mistura fungicida, composição agroquímica, uso não terapêutico da mistura e método para controlar fungos fitopatogênicos nocivos |
| EP3903582A1 (en) | 2020-04-28 | 2021-11-03 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ii |
| EP3903583A1 (en) | 2020-04-28 | 2021-11-03 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iii |
| EP3903581A1 (en) | 2020-04-28 | 2021-11-03 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors i |
| EP3903584A1 (en) | 2020-04-28 | 2021-11-03 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iv |
| EP4143167B1 (en) | 2020-04-28 | 2024-05-15 | Basf Se | Pesticidal compounds |
| EP3909950A1 (en) | 2020-05-13 | 2021-11-17 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP3945089A1 (en) | 2020-07-31 | 2022-02-02 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors v |
| WO2021249800A1 (en) | 2020-06-10 | 2021-12-16 | Basf Se | Substituted [1,2,4]triazole compounds as fungicides |
| EP3939961A1 (en) | 2020-07-16 | 2022-01-19 | Basf Se | Strobilurin type compounds and their use for combating phytopathogenic fungi |
| WO2022017836A1 (en) | 2020-07-20 | 2022-01-27 | BASF Agro B.V. | Fungicidal compositions comprising (r)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)propan-2-ol |
| EP3970494A1 (en) | 2020-09-21 | 2022-03-23 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii |
| AR123594A1 (es) | 2020-09-26 | 2022-12-21 | Pi Industries Ltd | Compuestos nematicidas y uso de los mismos |
| CN116209355A (zh) | 2020-10-27 | 2023-06-02 | 巴斯夫农业公司 | 包含氯氟醚菌唑的组合物 |
| WO2022090071A1 (en) | 2020-11-02 | 2022-05-05 | Basf Se | Use of mefenpyr-diethyl for controlling phytopathogenic fungi |
| WO2022090069A1 (en) | 2020-11-02 | 2022-05-05 | Basf Se | Compositions comprising mefenpyr-diethyl |
| WO2022106304A1 (en) | 2020-11-23 | 2022-05-27 | BASF Agro B.V. | Compositions comprising mefentrifluconazole |
| EP4018830A1 (en) | 2020-12-23 | 2022-06-29 | Basf Se | Pesticidal mixtures |
| AR124796A1 (es) | 2021-02-02 | 2023-05-03 | Basf Se | Acción sinérgica de dcd y alcoxipirazoles como inhibidores de la nitrificación |
| EP4043444A1 (en) | 2021-02-11 | 2022-08-17 | Basf Se | Substituted isoxazoline derivatives |
| EP4337012A1 (en) | 2021-05-11 | 2024-03-20 | Basf Se | Fungicidal mixtures comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles |
| AU2022279357A1 (en) | 2021-05-18 | 2023-11-30 | Basf Se | New substituted pyridines as fungicides |
| CN117355520A (zh) | 2021-05-18 | 2024-01-05 | 巴斯夫欧洲公司 | 用作杀真菌剂的新型取代喹啉类 |
| BR112023024017A2 (pt) | 2021-05-18 | 2024-02-06 | Basf Se | Compostos, composição, método para combater fungos fitopatogênicos e semente |
| WO2022243521A1 (en) | 2021-05-21 | 2022-11-24 | Basf Se | Use of ethynylpyridine compounds as nitrification inhibitors |
| AR125955A1 (es) | 2021-05-21 | 2023-08-30 | Basf Se | Uso de un compuesto de alcoxi pirazol n-funcionalizado como inhibidor de nitrificación |
| EP4094579A1 (en) | 2021-05-28 | 2022-11-30 | Basf Se | Pesticidal mixtures comprising metyltetraprole |
| WO2022268810A1 (en) | 2021-06-21 | 2022-12-29 | Basf Se | Metal-organic frameworks with pyrazole-based building blocks |
| EP4119547A1 (en) | 2021-07-12 | 2023-01-18 | Basf Se | Triazole compounds for the control of invertebrate pests |
| IL310497A (en) | 2021-08-02 | 2024-03-01 | Basf Se | (3-quinolyl)-quinazoline |
| WO2023011958A1 (en) | 2021-08-02 | 2023-02-09 | Basf Se | (3-pirydyl)-quinazoline |
| EP4140986A1 (en) | 2021-08-23 | 2023-03-01 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4140995A1 (en) | 2021-08-27 | 2023-03-01 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4151631A1 (en) | 2021-09-20 | 2023-03-22 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| WO2023072671A1 (en) | 2021-10-28 | 2023-05-04 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ix |
| WO2023072670A1 (en) | 2021-10-28 | 2023-05-04 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors x |
| EP4194453A1 (en) | 2021-12-08 | 2023-06-14 | Basf Se | Pyrazine compounds for the control of invertebrate pests |
| EP4198033A1 (en) | 2021-12-14 | 2023-06-21 | Basf Se | Heterocyclic compounds for the control of invertebrate pests |
| EP4198023A1 (en) | 2021-12-16 | 2023-06-21 | Basf Se | Pesticidally active thiosemicarbazone compounds |
| EP4238971A1 (en) | 2022-03-02 | 2023-09-06 | Basf Se | Substituted isoxazoline derivatives |
| WO2023203066A1 (en) | 2022-04-21 | 2023-10-26 | Basf Se | Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers |
| WO2024028243A1 (en) | 2022-08-02 | 2024-02-08 | Basf Se | Pyrazolo pesticidal compounds |
| EP4342885A1 (en) | 2022-09-20 | 2024-03-27 | Basf Se | N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides |
| EP4361126A1 (en) | 2022-10-24 | 2024-05-01 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xv |
| WO2024104813A1 (en) | 2022-11-14 | 2024-05-23 | Basf Se | Fungicidal mixture comprising substituted pyridines |
| WO2024104823A1 (en) | 2022-11-16 | 2024-05-23 | Basf Se | New substituted tetrahydrobenzoxazepine |
| WO2024104815A1 (en) | 2022-11-16 | 2024-05-23 | Basf Se | Substituted benzodiazepines as fungicides |
| WO2024104818A1 (en) | 2022-11-16 | 2024-05-23 | Basf Se | Substituted benzodiazepines as fungicides |
| WO2024104822A1 (en) | 2022-11-16 | 2024-05-23 | Basf Se | Substituted tetrahydrobenzodiazepine as fungicides |
| WO2024104814A1 (en) | 2022-11-16 | 2024-05-23 | Basf Se | Fungicidal mixture comprising substituted pyridines |
| EP4389210A1 (en) | 2022-12-21 | 2024-06-26 | Basf Se | Heteroaryl compounds for the control of invertebrate pests |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657524A (zh) * | 2004-02-20 | 2005-08-24 | 沈阳化工研究院 | 取代唑类化合物及其制备与应用 |
| CN1869034A (zh) * | 2005-05-26 | 2006-11-29 | 沈阳化工研究院 | 一种芳基醚类化合物及其制备与应用 |
| CN101323592A (zh) * | 2007-06-15 | 2008-12-17 | 沈阳化工研究院 | 取代苯基吡唑醚类化合物及其应用 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2773155B1 (fr) * | 1997-12-29 | 2000-01-28 | Rhone Poulenc Agrochimie | Nouveaux composes fongicides |
| JP4621939B2 (ja) * | 2004-03-31 | 2011-02-02 | イハラケミカル工業株式会社 | ５−ヒドロキシ−４−チオメチルピラゾール化合物の製造方法 |
-
2012
- 2012-05-10 CN CN201210144760.0A patent/CN103387541B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657524A (zh) * | 2004-02-20 | 2005-08-24 | 沈阳化工研究院 | 取代唑类化合物及其制备与应用 |
| CN1869034A (zh) * | 2005-05-26 | 2006-11-29 | 沈阳化工研究院 | 一种芳基醚类化合物及其制备与应用 |
| CN101323592A (zh) * | 2007-06-15 | 2008-12-17 | 沈阳化工研究院 | 取代苯基吡唑醚类化合物及其应用 |
Non-Patent Citations (1)
| Title |
|---|
| 新型杀菌剂唑菌酯吡唑环14C标记合成和鉴定;刘训悦 等;《化学学报》;20111231;第69卷(第12期);第1445-1449页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103387541A (zh) | 2013-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103387541B (zh) | 一种取代吡唑醚类化合物的制备方法 | |
| US8884033B2 (en) | Process for preparing aminobenzoylbenzofuran derivatives | |
| CA3022388C (en) | Method for preparing azoxystrobin intermediates | |
| EP3950660A1 (en) | Method for preparing dimethyl carbonate | |
| US10011557B2 (en) | Method for producing biphenylamines from azobenzenes by ruthenium catalysis | |
| TWI688558B (zh) | 一種亞托敏（Ａｚｏｘｙｓｔｒｏｂｉｎ）的製備方法 | |
| CN103387547B (zh) | 一种制备嘧螨胺的方法 | |
| CN108276356B (zh) | 3,5-二取代噻唑烷-2-硫酮类化合物制备方法 | |
| CN110218153A (zh) | 一种中间体化合物2,6-二乙基-4-甲基苯丙二酸酯的制备方法 | |
| CN110734368A (zh) | 一种布帕伐醌的制备方法 | |
| CN102850252B (zh) | 一种3,5,5’-三取代乙内酰脲的制备方法 | |
| CN114315609A (zh) | 一种制备顺式2-氨基环己醇的工艺方法 | |
| CN110878025B (zh) | 一种芳香类硝基化合物还原成芳香胺类化合物的方法 | |
| CN103387542B (zh) | 取代吡唑醚类化合物的制备方法 | |
| KR101316608B1 (ko) | 아연 촉매와 산을 이용한 글리세롤 카보네이트의 제조 방법 | |
| CN108084093B (zh) | 一锅法合成3-二氟甲基-1-甲基-1h-吡唑-4-羧酸的方法 | |
| KR102221534B1 (ko) | 치환된 감마 락탐의 합성을 위한 공정 | |
| US6596877B2 (en) | Accelerated process for preparing O-methyl phenols, N-methyl heteroaromatic compounds, and methylated aminophenols | |
| CN114456048B (zh) | 一种氯氟醚菌唑中间体的制备方法 | |
| CN109265431B (zh) | 3-乙酰基-10，11-二氢-5h-二苯并[c,g]色烯-8（9h）-酮合成工艺 | |
| EP3498690A1 (en) | Method for preparing intermediate of 6-arylaminopyridonecarboxamide compound as mek inhibitor | |
| CN101397291B (zh) | 2-氰乙酰-5-取代噻吩类化合物的制备方法 | |
| CN108658851B (zh) | 2-氯-3-甲基-6-酰基氨基吡啶及其制备方法和用途 | |
| CN115215815A (zh) | 一种高效制备噁唑烷酮衍生物的方法 | |
| CN103113265B (zh) | 一种由硝基化合物合成对称脲类化合物的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160202 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |