CN106008326A - 一种氢化诺卜基吡啶类季铵盐的合成方法 - Google Patents
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Abstract
本发明公开了一种氢化诺卜基吡啶类季铵盐的合成方法，在有机溶剂中，以氢化诺卜基卤代物和吡啶及其衍生物为原料，在冷凝回流的条件下，进行加热反应，反应后产物经抽滤、洗涤、重结晶、真空干燥纯化，分别合成得到七种氢化诺卜基吡啶类季铵盐；所述氢化诺卜基卤代物为氢化诺卜基氯、氢化诺卜基溴或氢化诺卜基碘；所述的吡啶及其衍生物为吡啶、α‑甲基吡啶、4‑甲基吡啶或4‑二甲氨基吡啶。本发明以氢化诺卜基卤代物和吡啶及其衍生物为原料，在冷凝回流及加热的条件下反应合成得到了七种氢化诺卜基吡啶类季铵盐。本发明的反应操作简便安全；反应条件温和、产物容易分离；目标产物得率优良，纯度较高。
Description
技术领域
本发明涉及精细有机合成技术领域，具体是一种氢化诺卜基吡啶类季铵盐的合成方法。
背景技术
季铵盐又称四级铵盐，从结构上可分为亲水的阳离子和疏水的长链，亲水部分用水可离解为一部分阳离子，从而可与其他表面活性剂复配，所以具有良好的复配作用。此外，它是一种阳离子表面活性剂，具有良好的吸附性和杀菌性等生物活性，对细菌、真菌、藻类和病毒等微生物都具有良好的杀生效果，被广泛地应用于众多领域，并且备受农药和医药界的广泛关注，其杀生机理与性能的研究一直以来都是国内外研究的热点，并取得了不少的新进展。
另一方面，我国松树资源非常丰富，其经蒸馏后得到的松节油产量大、价格低廉且是可再生资源，它的主要成分是α-蒎烯和β-蒎烯，其中β-蒎烯化学性质活泼，β-蒎烯及其衍生物显示出了广泛的生物活性。近年来，β-蒎烯已被广泛应用于用于香料、医药、食品、农业、高分子材料等行业中。在生物质资源化学与利用大潮的推动下，可再生资源β-蒎烯有着广泛的应用价值。通过对β-蒎烯的结构进行化学修饰合成具有生物活性的化合物已成为林产化学和有机合成化学的研究热点之一。
众多研究者对β-蒎烯开展了大量的研究，由其合成的诺卜醇、氢化诺卜醇及其醚类、酯类、缩醛类等衍生物对多种昆虫具有较好的拒食活性或较好的驱避活性。近年又合成了氢化诺卜酸及其酰胺类化合物，不同种类的初步活性测定表明，这些化合物具有一定的生理活性。为了对β-蒎烯衍生物进行更加深入的活性筛选及其相关研究，有必要增加此类化合物的品种和数量。因此，本专利公开了一种合成氢化诺卜基吡啶类季铵盐的方法。
发明内容
本发明的目的在于提供一种产物容易分离、纯度高的氢化诺卜基吡啶类季铵盐的合成方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种氢化诺卜基吡啶类季铵盐的合成方法，在有机溶剂中，以氢化诺卜基卤代物和吡啶及其衍生物为原料，在冷凝回流的条件下，进行加热反应，反应后产物经抽滤、洗涤、重结晶、真空干燥纯化，分别合成得到七种氢化诺卜基吡啶类季铵盐。
作为本发明进一步的方案：所述有机溶剂是温度为60-90℃的石油醚。
作为本发明进一步的方案：所述的氢化诺卜基卤代物与吡啶及其衍生物的摩尔比为1∶1.5-2.0。
作为本发明进一步的方案：所述加热反应的反应温度为70-75℃，加热反应的反应时间为1-2d。
作为本发明进一步的方案：所述氢化诺卜基卤代物为氢化诺卜基氯、氢化诺卜基溴或氢化诺卜基碘。
作为本发明进一步的方案：所述的吡啶及其衍生物为吡啶、α-甲基吡啶、4-甲基吡啶或4-二甲氨基吡啶。
作为本发明进一步的方案：所述氢化诺卜基溴分别与吡啶、4-甲基吡啶和4-二甲氨基吡啶进行反应，制得三种含氢化诺卜基溴化吡啶类化合物。
作为本发明进一步的方案：所述氢化诺卜基氯与吡啶反应制得含氢化诺卜基氯化吡啶。
作为本发明再进一步的方案：所述氢化诺卜基碘分别与吡啶、α-甲基吡啶和4-甲基吡啶进行反应，制得三种含氢化诺卜基碘化吡啶类化合物。
与现有技术相比，本发明的有益效果是：
本发明以氢化诺卜基卤代物和吡啶及其衍生物为原料，在冷凝回流及加热的条件下反应合成得到了七种氢化诺卜基吡啶类季铵盐。本发明的反应操作简便安全；反应条件温和、产物容易分离；目标产物得率优良，纯度较高。
具体实施方式
下面结合具体实施方式对本专利的技术方案作进一步详细地说明。
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基卤化物、0.02mol吡啶及其衍生物、温度为60-90℃的石油醚，在70-75℃下加热1-2d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到产物。
实施例1
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基溴、0.02mol吡啶、温度为60℃的石油醚，在70℃下加热1d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到N-氢化诺卜基溴化吡啶。
实施例2
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基氯、0.02mol吡啶、温度为65℃的石油醚，在70℃下加热1.1d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到N-氢化诺卜基氯化吡啶。
实施例3
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基碘、0.02mol吡啶、温度为70℃的石油醚，在71℃下加热1.2d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到N-氢化诺卜基碘化吡啶。
实施例4
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基碘、0.02mol的α-甲基吡啶、温度为75℃的石油醚，在72℃下加热1.5d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到α-甲基-N-氢化诺卜基碘化吡啶。
实施例5
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基溴、0.02mol的4-二甲氨基吡啶、温度为80℃的石油醚，在73℃下加热1.6d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到γ-(N，N-二甲基)-N-氢化诺卜基溴化吡啶。
实施例6
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基碘、0.02mol的4-二甲氨基吡啶、温度为85℃的石油醚，在74℃下加热1.8d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到γ-(N，N-二甲基)-N-氢化诺卜基碘化吡啶。
实施例7
一种氢化诺卜基吡啶类季铵盐的合成方法，在装有冷凝回流装置和搅拌子的100mL的锥形瓶中加入约0.01mol氢化诺卜基溴、0.02mol的4-甲基吡啶、温度为90℃的石油醚，在75℃下加热2d，冷却结晶，过滤出固体，并用石油醚淋洗，重结晶，真空干燥，得到γ-甲基-N-氢化诺卜基溴化吡啶。
本发明以氢化诺卜基卤代物和吡啶及其衍生物为原料，在冷凝回流及加热的条件下反应合成得到了七种氢化诺卜基吡啶类季铵盐。本发明的反应操作简便安全；反应条件温和、产物容易分离；目标产物得率优良，纯度较高。
上面对本专利的较佳实施方式作了详细说明，但是本专利并不限于上述实施方式，在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本专利宗旨的前提下作出各种变化。
Claims (9)
1.一种氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，在有机溶剂中，以氢化诺卜基卤代物和吡啶及其衍生物为原料，在冷凝回流的条件下，进行加热反应，反应后产物经抽滤、洗涤、重结晶、真空干燥纯化，分别合成得到七种氢化诺卜基吡啶类季铵盐。
2.根据权利要求1所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述有机溶剂是温度为60-90℃的石油醚。
3.根据权利要求1所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述的氢化诺卜基卤代物与吡啶及其衍生物的摩尔比为1：1.5-2.0。
4.根据权利要求1所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述加热反应的反应温度为70-75℃，加热反应的反应时间为1-2d。
5.根据权利要求1所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述氢化诺卜基卤代物为氢化诺卜基氯、氢化诺卜基溴或氢化诺卜基碘。
6.根据权利要求1所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述的吡啶及其衍生物为吡啶、α-甲基吡啶、4-甲基吡啶或4-二甲氨基吡啶。
7.根据权利要求5-6任一所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述氢化诺卜基溴分别与吡啶、4-甲基吡啶和4-二甲氨基吡啶进行反应，制得三种含氢化诺卜基溴化吡啶类化合物。
8.根据权利要求5-6任一所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述氢化诺卜基氯与吡啶反应制得含氢化诺卜基氯化吡啶。
9.根据权利要求5-6任一所述的氢化诺卜基吡啶类季铵盐的合成方法，其特征在于，所述氢化诺卜基碘分别与吡啶、α-甲基吡啶和4-甲基吡啶进行反应，制得三种含氢化诺卜基碘化吡啶类化合物。
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| CN110172026A (zh) * | 2018-12-26 | 2019-08-27 | 江西农业大学 | 一种双氢化诺卜基的季铵盐的合成方法与抗菌应用 |
| CN110172026B (zh) * | 2018-12-26 | 2021-08-24 | 江西农业大学 | 一种双氢化诺卜基的季铵盐的合成方法与抗菌应用 |
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