CN103936723B - 一种催化三唑烯环氧化制备氟环唑的方法 - Google Patents

一种催化三唑烯环氧化制备氟环唑的方法 Download PDF

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CN103936723B
CN103936723B CN201310024555.5A CN201310024555A CN103936723B CN 103936723 B CN103936723 B CN 103936723B CN 201310024555 A CN201310024555 A CN 201310024555A CN 103936723 B CN103936723 B CN 103936723B
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姜鹏
孟志
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J2531/72—Manganese

Abstract

本发明涉及农药领域，具体地讲是一种催化三唑烯环氧化制备氟环唑的方法。将配体与锰离子原位形成活性催化物种与底物三唑烯在充分搅拌溶解后置于-10-60℃，再加入三唑烯摩尔量的5-8倍的氧化剂反应6-24小时，即得到氟环唑。本发明的催化剂制备简单，廉价，应用于催化三唑烯合成氟环唑时，化学选择性高，所需双氧水浓度低，收率高、稳定性好，反应条件温和，所用溶剂绿色环保、无毒或低毒。

Description

一种催化三唑烯环氧化制备氟环唑的方法
技术领域
本发明涉及农药领域，具体地讲是一种催化三唑烯环氧化制备氟环唑的方法。
背景技术
氟环唑是一种高效、低毒、低残留的广谱性三唑类杀菌剂，由德国巴斯夫公司1985年开发。文献报道氟环唑原药有六条合成路线，工业生产中采用三唑烯合成氟环唑。专利U.S.5245042采用马来酸酐与双氧水原位形成单过氧马来酸对三唑烯进行环氧化，该工艺方法采用三唑烯摩尔量的10倍马来酸酐，相当于生产1吨氟环唑产生3.52吨马来酸，大量废酸的产生增加了后处理步骤，也给环境带来了巨大压力；同时该工艺路线采用质量浓度为50％的双氧水，高浓度双氧水的使用在生产中存在巨大的安全隐患；而且此工艺路线采用环境不友好的二氯乙烷作为溶剂。有人报道以8-羟基喹啉锰的配合物催化烯烃环氧化反应（ZL200610136989.4），此方法催化剂需提前制备，而且此催化体系仅对简单的、富电子的烯烃有比较好的效果，对三唑烯这种大位阻、缺电子的烯烃催化效果比较差。
发明内容
本发明的目的在于提供一种催化三唑烯环氧化制备氟环唑的方法。
为实现上述目的，本发明采用的技术方案为：
一种催化三唑烯环氧化制备氟环唑的方法，将由配体与锰离子原位形成活性催化物与底物三唑烯在充分搅拌溶解后于-10-60℃，再加入三唑烯摩尔量的5-8倍的氧化剂反应6-24小时，即得到氟环唑。
所述催化物由通式（I）的8-羟基喹啉衍生物为第一配体、以通式（II）吡唑类衍生物为第二配体与锰离子原位形成活性催化物；
通式（I）中芳环上的取代基R1、R2、R3、R5和R6为H，R4为卤素；通式（II）中吡唑环上R1＇，R2＇，R3＇，R4＇，分别可为氢、卤素、烷基、硝基或氰基；所述锰离子为醋酸锰（III）或乙酰丙酮锰（III）三价锰离子。
所述通式（II）中R1＇=R2＇=R3＇=Ｒ4＇=H或R1＇=R3＇=R4＇=H，R2＇=CH3。
所述三价锰离子（简写为Mn（III））、8-羟基喹啉衍生物（简写为8-HQ）、吡唑类衍生物（简写为Pyz）摩尔比为Mn（III）：8-HQ：Pyz=1:1～5:1～50。Mn（III）：8-HQ：Pyz=1:2～3:20～30.
将配体溶于有机溶剂中在与锰离子原位形成活性催化物；所述有机溶剂为酮、醇、水、氯代烃、酯、腈中的一种几种的混合。
所述有机溶剂为丁酮、丙酮、丁二酮或乙腈。
所述氧化剂为质量浓度为10-50％的双氧水。所述氧化剂为质量浓度为30-50％的双氧水。
所述反应温度在-5-20℃。
本发明的优点是：
1.本发明催化剂成本低、并且采用原位制备方法制备工艺简单，催化剂环氧化效率高、稳定性好，反应条件温和；所用溶剂绿色环保，无毒或低毒；杜绝了酸酐的使用，减化了后处理步骤；所用氧化剂双氧水浓度低，收率高，解决了工业生产中的安全隐患问题。
2.本发明简便高效的由三唑烯通过催化环氧化来制备氟环唑原药的方法，以杜绝过量废酸的产生，简化后处理步骤，减小环境压力；同时采用低浓度双氧水，解决实际生产过程中的安全隐患问题。本发明催化剂催化效率高、化学选择性好、廉价、制备工艺简单，反应条件温和，所用溶剂绿色环保。
具体实施方式
以下所述实施例用于进一步详细说明本发明。在这些实施例中，除非有特殊声明，所用8-羟基喹啉及其衍生物、吡唑及其衍生物、锰盐、三唑烯均已毫摩尔（mmol）计量，丙酮以毫升（mL）计量。
实施例1：
将0.02mmol乙酰丙酮锰（III）、0.06mmol8-羟基喹啉、0.6mmol吡唑加入烧瓶中，加入5mL丙酮搅拌均匀后，然后再加入1mmol三唑烯。室温搅拌10分钟后，反应温度降至0℃左右，将8mmol质量分数为30％的双氧水溶液逐滴加入上述丙酮溶液中，3小时滴加完毕，然后自然升温至室温反应8小时。得氟环唑粗品，收率为74.2％，采用安捷伦1200-HPLC检测纯度为91.3％（检测波长为205nm，流动相为乙腈和水50:50，C18色谱柱）。
实施例2：
将0.02mmol乙酰丙酮锰（III）、0.06mmol5-氯-8-羟基喹啉、0.6mmol吡唑加入烧瓶中，加入5mL丙酮搅拌均匀后，然后再加入1mmol三唑烯。室温搅拌10分钟后，反应温度降至0℃左右，将8mmol质量分数为30％的双氧水溶液逐滴加入上述丙酮溶液中，3小时滴加完毕，然后自然升温至室温反应8小时。处理得氟环唑粗品，收率为69.2％，采用安捷伦1200-HPLC检测纯度为90.8％（检测波长为205nm，流动相为乙腈和水50:50，C18色谱柱）。
实施例3：
将0.02mmol乙酰丙酮锰（III）、0.06mmol8-羟基喹啉、0.6mmol3-甲基吡唑加入烧瓶中，加入5ml丙酮搅拌均匀后，然后再加入1mmol三唑烯。室温搅拌10分钟后，反应温度降至0℃左右，将8mmol质量分数为30％的双氧水溶液逐滴加入上述丙酮溶液中，3小时滴加完毕，然后自然升温至室温反应8小时。处理得氟环唑粗品，收率为72.8％，采用安捷伦1200-HPLC检测纯度为91.0％（检测波长为205nm，流动相为乙腈和水50:50，C18色谱柱）。
上述所得氟环唑产品核磁1H-NMR(300MHz,CDCl3),δ:7.86(s,1H,azolyl-H),7.78(s,1H,azolyl-H),7.01-7.60(m,8H,Ar-H),4.72-4.76(d,1H,15Hz,CH2),4.24(s,1H,CH),3.95-4.00(d,1H,15Hz,CH2)，其化学位移、耦合常数及其峰面积比值与标准品一致。
对比实施例1
参考ZL200610136989.4专利制备8-羟基喹啉锰催化剂。按照实施例1所述方法进行操作，即将0.03mmol的8-羟基喹啉锰催化剂加入到5mL丙酮溶液中搅拌，然后再加入1mmol三唑烯，室温搅拌10分钟后，反应温度降至0℃左右，将8mmol质量分数为30％的双氧水溶液逐滴加入上述丙酮溶液中，3小时滴加完毕，然后自然升温至室温反应8小时。处理得氟环唑粗品，收率为56.2％，采用安捷伦1200-HPLC检测纯度为80.8％（检测波长为205nm，流动相为乙腈和水50:50，C18色谱柱）。
对比实施例2
参考ZL200610136989.4专利制备8-羟基喹啉锰催化剂。按照实施例1所述方法进行操作，即将0.03mmol的8-羟基喹啉锰催化剂加入到5mL丙酮溶液中搅拌，然后再加入1mmol三唑烯，室温搅拌10分钟后，然后加入ZL200610136989.4中所述助剂（0.2mmolNH4OAc和0.1mmolHOAc的水溶液1mL），反应温度降至0℃左右，将8mmol质量分数为30％的双氧水溶液逐滴加入上述丙酮溶液中，3小时滴加完毕，然后自然升温至室温反应8小时。处理得氟环唑粗品，收率为27.1％，采用安捷伦1200-HPLC检测纯度为30.8％（检测波长为205nm，流动相为乙腈和水50:50，C18色谱柱）。
对比实施例3
参考ZL200610136989.4专利制备8-羟基喹啉锰催化剂。按照实施例1所述方法进行操作，即将0.03mmol的8-羟基喹啉锰催化剂加入到5mL丙酮溶液中搅拌，然后再加入1mmol三唑烯，室温搅拌10分钟后，然后加入ZL200610136989.4中所述助剂（0.2mmol咪唑的水溶液1mL），反应温度降至0℃左右，将8mmol质量分数为30％的双氧水溶液逐滴加入上述丙酮溶液中，3小时滴加完毕，然后自然升温至室温反应8小时。处理得氟环唑粗品，收率为21.3％，采用安捷伦1200-HPLC检测纯度为24.2％（检测波长为205nm，流动相为乙腈和水50:50，C18色谱柱）。
本发明专利中催化剂制备采用原位制备方法，制备工艺简单，对催化环氧化制备氟环唑有很好的催化效果；从对比实施例中可以看出采用现有技术对氟环唑环氧化在不加添加剂的情况下，选择性不好，有大量副产产生，收率仅为56.2％（对比实施例1）；加入添加剂，转化率较低，收率不到30％（对比实施例2、3）。本发明专利对氟环唑这个特定的大位阻、极度缺电子的烯烃有很好的催化效果，收率能达到70％以上。

Claims (8)

1.一种催化三唑烯环氧化制备氟环唑的方法，其特征在于：将由配体与锰离子原位形成活性催化物与底物三唑烯在充分搅拌溶解后于-10～60℃，再加入三唑烯摩尔量的5～8倍的氧化剂反应6～24小时，即得到氟环唑；
所述催化物由通式(I)的8-羟基喹啉衍生物为第一配体、以通式(II)吡唑类衍生物为第二配体与锰离子原位形成活性催化物；
通式(I)中芳环上的取代基R1、R2、R3、R5和R6为H，R4为卤素；通式(II)中吡唑环上R1＇，R2＇，R3＇，R4＇，分别为氢、卤素、硝基或氰基；或通式(II)中R1＇＝R3＇＝R4＇＝H，R2＇＝CH3；
所述锰离子为醋酸锰或乙酰丙酮锰三价锰离子。
2.按权利要求1所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于：所述三价锰离子简写为Mn3+、8-羟基喹啉衍生物简写为8-HQ、吡唑类衍生物简写为Pyz，摩尔比为Mn3+：8-HQ：Pyz＝1:1～5:1～50。
3.按权利要求2所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于所述：Mn3+：8-HQ：Pyz＝1:2～3:20～30。
4.按权利要求1所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于：将配体溶于有机溶剂中在与锰离子原位形成活性催化物；所述有机溶剂为酮、醇、水、氯代烃、酯、腈中的一种几种的混合。
5.按权利要求4所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于：所述有机溶剂为丁酮、丙酮、丁二酮或乙腈。
6.按权利要求1所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于：所述氧化剂为质量浓度为10～50％的双氧水。
7.按权利要求6所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于：所述氧化剂为质量浓度为30～50％的双氧水。
8.按权利要求1所述的催化三唑烯环氧化制备氟环唑的方法，其特征在于：所述反应温度在-5～20℃。
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