CN110694692B - 一种空气稳定型催化剂及其制备和催化生成n1-取代吡唑类衍生物的应用 - Google Patents

一种空气稳定型催化剂及其制备和催化生成n1-取代吡唑类衍生物的应用 Download PDF

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CN110694692B
CN110694692B CN201810744472.6A CN201810744472A CN110694692B CN 110694692 B CN110694692 B CN 110694692B CN 201810744472 A CN201810744472 A CN 201810744472A CN 110694692 B CN110694692 B CN 110694692B
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姜鹏
朱琳娜
王嫱
于海波
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Abstract

本发明涉及农药和医药领域，具体地是制备一种在空气中稳定的催化剂及其制备和催化生成N1‑取代的吡唑类衍生物的应用。化剂为结构式(Ⅱ)所示化合物；所述的催化剂在催化合成N1‑取代吡唑类衍生物中的应用。本发明的催化剂制备简单、廉价、稳定，应用于催化吡唑类化合物与含卤素芳环或杂环时，应用范围广，制备简单、收率高、反应条件温和，所用溶剂绿色环保、无毒或低毒。

Description

一种空气稳定型催化剂及其制备和催化生成N1-取代吡唑类 衍生物的应用
技术领域
本发明涉及农药和医药领域，具体地是制备一种在空气中稳定的催化剂及其制备和催化生成N1-取代的吡唑类衍生物的应用。
背景技术
吡唑类化合物作为含氮杂环体系中的重要一员，不但具有着独特的结构形式，而且具有广谱的生物活性，在杀虫、除草、杀菌及抗癌等方面发挥着重要的作用。由N1-取代的吡唑类衍生物在农药和医药领域有着广泛的应用，如1947年瑞士汽巴-嘉基公司上市的杀虫剂吡虫威(pyrolan)；1979年巴斯夫公司上市的吡唑类除草剂吡草胺 (metazachlor)；1999年美国Searle制药厂研发上市用于治疗风湿性、类风湿性及骨关节炎的塞来考昔(celecoxib)；2001年Selwood等人报道的具有活化可溶性钠尿肽鸟苷酸环化酶以及抑制血小板凝结的芳基取代吡唑类化合物。
文献报道的N1-取代的吡唑类衍生物可由β-酮基酯及类似物与肼类衍生物合成，该方法虽方便易行但过程过于繁琐，不利于反应的多样化。 2017年，Adrian Huang，KellieWO等人提出一种无催化剂生成N1-取代的吡唑类衍生物的方法，该方法虽然高效但对反应物的要求苛刻，仅适用于3位强吸电子基团取代的吡唑类化合物与氟取代或个别溴取代的芳环或杂环的合成，生产成本高，所适用的范围窄。因此，开发一种广谱高效且廉价易得的催化合成N1-取代吡唑类衍生物的催化剂十分必要。
发明内容
本发明的目的在于利用廉价易得的市售商品制备催化合成N1-取代吡唑类衍生物的催化剂及其制备和催化生成N1-取代吡唑类衍生物的应用。
为实现上述目的，本发明采用技术方案为：
一种空气稳定型催化剂，催化剂为结构式(Ⅱ)所示化合物
Figure BDA0001723986660000011
一种空气稳定型催化剂的制备方法：
Figure BDA0001723986660000021
将溴化镍与4,5-双二苯基膦-9,9-二甲基氧杂蒽，在氮气条件下加热回流 30-60分钟，旋干得深绿色固体式(Ⅰ)化合物，氮气条件下，将式(Ⅰ) 化合物在0℃下滴加2,4,6-三甲基苯基溴化镁，升至室温，反应30-60分钟，旋干后得红棕色固体式(Ⅱ)，反应式如上。
进一步的说，将溴化镍与4,5-双二苯基膦-9,9-二甲基氧杂蒽，在氮气条件下加热回流30-60分钟后，冰浴条件下冷却至0℃，抽滤、洗涤，再经二氯甲烷冲洗，收集冲洗液，旋干得深绿色固体，即结构式(Ⅰ) 化合物，氮气条件下，将式(Ⅰ)化合物在0℃下滴加2,4,6-三甲基苯基溴化镁，升至室温，反应30-60分钟、抽滤抽滤、洗涤，再经二氯甲烷冲洗，收集冲洗液，旋干后得红棕色固体，即结构式(Ⅱ)，反应式如上。
所述溴化镍与4,5-双二苯基膦-9,9-二甲基氧杂蒽的摩尔比为：1：1；式(Ⅰ)化合物与2,4,6-三甲基苯基溴化镁的摩尔比为：1:1。
一种催化剂在催化合成N1-取代吡唑类衍生物中的应用。
反应式为：
Figure BDA0001723986660000022
吡唑类化合物、卤素取代的芳环或杂环、碱性物质、催化剂(Ⅱ)在有机溶剂中，氮气条件下，加热回流反应5-7小时(回流反应根据有机溶剂温度为20-100℃，优选50-80℃)，或室温反应16-24小时，合成N1- 取代吡唑类衍生物。
所述催化剂结构式(Ⅱ)的用量为吡唑类化合物摩尔量的1-20mol％，碱性物质的用量为吡唑类化合物摩尔量的100-150mol％。
所述卤素取代的芳环或杂环为氯、溴取代的芳环或杂环；所述有机溶剂为四氢呋喃、甲基四氢呋喃；所述吡唑类化合物为无取代吡唑或甲基吡唑、三氟甲基吡唑或硝基吡唑。
所述碱性物质为固体碱；固体碱为甲醇钠、叔丁醇钾、碳酸钾、氢氧化钾或氢氧化钠，优选甲醇钠或叔丁醇钾。
本发明所具有的优点：
本发明催化剂成本低、制备工艺简单，催化剂催化效率高、稳定性好、反应条件温和、空气中稳定，适用范围广，可进一步适用于催化氯、溴等活性较低的卤素取代杂环与吡唑类化合物的合成、所用溶剂绿色环保，无毒或低毒。
附图说明
图1为本发明实施例提供的催化剂核磁谱图，1H NMR(300MHz, CDCl3)。
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，所用药品均以毫摩尔(mmol)计量，溶剂均以毫升(mL) 计量。产物均经LC-MS验证，检测条件为乙腈：水＝50:50，10分钟后 80:20，流速0.8mL/min，30℃，12min，RP-C18柱。回流温度依反应物和碱量不同而不同，反应温度在60-75℃之间。
实施例1：
反应式：
Figure BDA0001723986660000031
将10mmol溴化镍放入烘干的三颈圆底烧瓶中，加入60mL无水乙醇，随后加入10mmol 4,5-双二苯基膦-9,9-二甲基氧杂蒽。在氮气条件下加热回流30分钟后，冰浴条件下冷却至0℃。抽滤，依次用冷的无水乙醇、***各冲洗3次。最后用二氯甲烷冲洗，收集冲洗液，旋干得深绿色固体—结构式(Ⅰ)所示化合物，收率为89.6％。
Figure BDA0001723986660000032
在氮气条件下，将8mmol的式(Ⅰ)所示化合物与40mL干燥处理后的四氢呋喃加入干燥的圆底烧瓶中，在0℃下滴加8mmol 2,4,6-三甲基苯基溴化镁。滴加完毕后，升至室温，反应30分钟。旋干溶剂，加入 30mL冷的无水乙醇，抽滤，依次用冷的无水乙醇、石油醚冲洗各冲洗3 次。最后用二氯甲烷冲洗，收集冲洗液，旋干后得红棕色固体—结构式 (Ⅱ)所示催化剂(参见图1)，收率为97.2％。
实施例2：
反应式：
Figure BDA0001723986660000033
在圆底烧瓶中加入6.58g吡唑、3.4g氯化苄、0.84g结构式(Ⅱ) 所示催化剂、5.52g叔丁醇钾、70mL四氢呋喃，氮气条件下加热回流7 小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:4)，得6.60 g无色液体，收率为83.4％。
实施例3：
反应式：
Figure BDA0001723986660000041
在圆底烧瓶中加入0.57g 3-硝基吡唑、0.89g氯化苄、0.21g结构式 (Ⅱ)所示催化剂、0.56g叔丁醇钾、50mL四氢呋喃，氮气条件下加热回流7小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:2)，得0.73g黄色液体，收率为71.9％。
实施例4：
反应式：
Figure BDA0001723986660000042
在圆底烧瓶中加入1.70g 3-三氟甲基吡唑、2.00g氯化苄、0.42g结构式(Ⅱ)所示催化剂、1.40g叔丁醇钾、60mL四氢呋喃，氮气条件下加热回流7小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:2)，得2.66g浅黄色液体，收率为94.1％。
实施例5：
反应式：
Figure BDA0001723986660000043
在圆底烧瓶中加入0.41g 3-甲基吡唑、0.89g氯化苄、0.21g结构式 (Ⅱ)所示催化剂、0.56g叔丁醇钾、50mL四氢呋喃，氮气条件下加热回流7小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:2)，得0.75g黄色液体，收率为87.2％。
实施例6：
反应式：
Figure BDA0001723986660000044
在圆底烧瓶中加入1.70g吡唑、4.80g溴化苄、0.42g结构式(Ⅱ) 所示催化剂、2.80g叔丁醇钾、50ml四氢呋喃，氮气条件下室温反应24 小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:4)，得3.02 g无色液体，收率为76.5％。
实施例7：
反应式：
Figure BDA0001723986660000045
在圆底烧瓶中加入0.68g吡唑、1.27g氯化苄、0.42g结构式(Ⅱ) 所示催化剂、0.54g甲醇钠、50mL四氢呋喃，氮气条件下加热回流7小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:4)，得0.49g 无色液体，收率为31.0％。
实施例8：
反应式：
Figure BDA0001723986660000051
在圆底烧瓶中加入0.57g 4-硝基吡唑、0.89g氯化苄、0.21g结构式 (Ⅱ)所示催化剂、0.56g叔丁醇钾、50mL四氢呋喃，氮气条件下回流 5小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:2)，得0.98 g黄色液体，收率为95.7％。
实施例9：
反应式：
Figure BDA0001723986660000052
在圆底烧瓶中加入0.34g吡唑、1.03g对硝基氯化苄、0.21g结构式 (Ⅱ)所示催化剂、0.56g叔丁醇钾、50mL四氢呋喃，氮气条件下回流 7小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:2)，得0.95g 黄色固体，收率为93.6％。
实施例10：
反应式：
Figure BDA0001723986660000053
在圆底烧瓶中加入0.68g吡唑、1.58g对氯硝基苯、0.42g结构式(Ⅱ) 所示催化剂、1.35g叔丁醇钾、50mL四氢呋喃，氮气条件下回流7小时。过滤，滤液旋干后过柱(乙酸乙酯：石油醚(v/v)＝1:2)，得0.57g黄色油状液体，收率为30.2％。

Claims (5)

1.一种空气稳定型催化剂在催化合成N1-取代吡唑类衍生物中的应用，其特征在于：催化剂为结构式(Ⅱ)所示化合物
Figure FDA0003132796310000011
2.按权利要求1所述的催化剂在催化合成N1-取代吡唑类衍生物中的应用，其特征在于：
反应式为：
Figure FDA0003132796310000012
吡唑类化合物、卤素取代的芳环或杂环、碱性物质、催化剂(Ⅱ)在有机溶剂中，氮气条件下，加热回流反应5-7小时，或室温反应16-24小时，合成N1-取代吡唑类衍生物。
3.按权利要求2所述的催化剂在催化合成N1-取代吡唑类衍生物中的应用，其特征在于：所述催化剂结构式(Ⅱ)的用量为吡唑类化合物摩尔量的1-20mol％，碱性物质的用量为吡唑类化合物摩尔量的100-150mol％。
4.按权利要求2所述的催化剂在催化合成N1-取代吡唑类衍生物中的应用，其特征在于：所述卤素取代的芳环或杂环为氯、溴取代的芳环或杂环；所述有机溶剂为四氢呋喃、甲基四氢呋喃；所述吡唑类化合物为无取代吡唑或甲基吡唑、三氟甲基吡唑或硝基吡唑。
5.按权利要求2所述的催化剂在催化合成N1-取代吡唑类衍生物中的应用，其特征在于：所述碱性物质为固体碱；固体碱为甲醇钠、叔丁醇钾、碳酸钾、氢氧化钾或氢氧化钠。
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