CN112409145B - 一种1-四氢萘酮的制备方法 - Google Patents
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Abstract
本发明提供一种1‑四氢萘酮的制备方法,包括:雷尼镍催化下,反应温度为170~250℃,反应压力为3.0~5.0Mpa,1‑萘酚与氢气发生加氢反应,得含有1‑四氢萘酮的混合物。本发明的制备方法,采用廉价的1‑萘酚与氢气进行加氢反应,通过控制加氢反应温度,有效减少了加氢反应的主要产物种类,降低了目标产物的分离难度。之后根据加氢反应后混合物中各物质的性质,依次采用多次碱洗和水洗,最后精馏的方式分离出纯度较高的目标产物1‑四氢萘酮。本发明的制备方法,工艺简单,操作方便,加氢反应转化率高,反应过程无废水产生,原料和加工成本低。
Description
技术领域
本发明属于医药技术领域,具体涉及一种1-四氢萘酮的制备方法。
背景技术
1-四氢萘酮主要用于合成18-甲基炔诺酮(避孕药)、杀鼠剂的中间体,也是合成苯那普利的重要中间体。此外,它还可用作溶剂和塑料的软化剂。目前四氢萘酮生产方法主要有四种:
1.四氢萘氧化法
这种方法采用乙酸铬和2-甲基-5-乙基吡啶复合催化剂,加氧气氧化制得,主要问题是单程转化率较低,容易产生2-四氢萘酮等杂质。
2.γ-丁内酯与苯缩合而得
这种方法主要问题是处理三氯化铝产生大量的三氯化铝废水。
3.γ-苯丁酸环化法γ-苯丁酸在磷酸/磷酸酐、多磷酸、氢氟酸或浓硫酸作用下,在90℃环化得到1-四氢萘酮。
这种方制备方法主要是原料γ-苯丁酸比较贵,成本高,并且产生大量的废水。
4.γ-苯丁酰氯环化法在无水三氯化铝或无水四氯化锡存在下脱氯化氢环化得本品。
这种方制备方法主要是原料γ-苯丁酰氯比较贵,成本高,并且产生大量的三氯化铝废水或者四氯化锡废水。
同时文献(张晶蕾等:用铝-镍合金还原1-萘酚反应的再研究,有机化学,2008年,第28卷,第4期,723~726)报道以铝-镍合金还原1-萘酚(1)制备5,6,7,8-四氢-1-萘酚(2)时,得到了与文献不同的结果:除获得了少量2外,意外地获得了大量的3,4-二氢-2H-萘-1-酮(3)和1,2,3,4-四氢-1-萘酚(4):
其中1-四氢萘酮(即3,4-二氢-2H-萘-1-酮(3))的收率在37~48%之间,得到的化合物2~4需要通过柱层析进行分离,一方面收率不理想,同时采用柱层析无法实现工业化大量生产。另外,产物中,化合物3和化合物4沸点比较接近,单纯靠精馏的办法无法将目标产物(3)完全分离。
综上所述,现有技术中的1-四氢萘酮的制备方法存在转化率和纯度较低,原料成本较高,且产生大量废水,处理难度大,成本高等问题。
发明内容
为解决上述现有技术中存在的问题,本发明提供一种1-四氢萘酮的制备方法,其转化率和纯度高,原料成本低,且制备过程无大量废水产生,生产成本低。
本发明在按照文献的方法,用1-萘酚在雷尼镍催化剂制备5,6,7,8-四氢-1-萘酚的合成过程中,合成了1-四氢萘酮和1,2,3,4-四氢-1-萘酚,并且在多次实验下获得了制备了1-四氢萘酮的方法。
一种1-四氢萘酮的制备方法,包括:
雷尼镍催化下,反应温度为170~250℃,反应压力为3.0~5.0Mpa,1-萘酚与氢气发生加氢反应,得含有1-四氢萘酮的混合物,经后处理得所述1-四氢萘酮。
一般1-萘酚加氢反应中,反应的主要产物有(1)5,6,7,8-四氢萘-1-酚、(2)1-四氢萘酮和(3)1,2,3,4-四氢萘-1-酚,具体反应过程如下:
在各种条件下,这几种产物都共存,只是比例不一样而已。在进一步的实验中发现,产物(2)会进一步转化成(3),而产物(3)也会进一步转化成四氢萘(4),甚至在极端条件下,萘上另一个环也会进一步开环加氢。
当反应温度低于150℃时,产物(3)占优势,产物(4)比较少,当反应温度提高到150~170℃时,产物(3)大部分转化为产物(4),当反应温度170℃以上时,产物(3)会很少,大部分都是产物(4)存在。
加氢反应后的混合物中还可能存在未反应的1-萘酚,由于1-萘酚,产物(2)、(3)、(4)四个物料的沸点比较接近,单纯靠精馏的办法无法将目标产物(2)完全分离。
上述制备方法控制加氢反应温度为170~250℃,使产物(3)全部转化成产物(4),再利用产物(1)和没有反应的原料1-萘酚溶于一定量的碱中的特性,将上述混合物进行碱洗,把原料1-萘酚和产物(1)从混合物中分离出来,然后经过进一步精馏则可以分离出纯的目标产物(2)1-四氢萘酮,其纯度高达98%以上。
步骤(1)中:
作为优选,所述加氢反应在无溶剂状态下进行,此时1-萘酚兼做反应产物和溶剂,进一步降低了后续溶剂的回收难度。
所述加氢反应也可以在有机溶剂中进行,所述有机溶剂优选为甲苯和二甲苯中的一种或二者的混合;进一步优选为甲苯。1-萘酚与所述有机溶剂的质量体积比为(0.25~1)g/ml;进一步优选为(0.25~0.5)g/ml;更进一步优选为0.25g/ml。
作为优选,所述加氢反应温度为200~250℃,使产物(3)尽可能地全部转化成产物(4)。
作为优选,所述加氢反应在压力釜内进行,通入氢气前先通入氮气置换2~5次,以除去压力釜内的空气,提高加氢反应的效率。
作为优选,所述加氢反应时间为7~20小时。
作为优选,雷尼镍与所述1-萘酚的质量比为(0.01~0.05):1;进一步优选为(0.01~0.03):1。
作为具体优选,步骤(1)的操作过程为:
将1-萘酚溶于溶剂中并添加到压力釜内,随后加入催化剂,并通入氮气置换2~5次;随后通入氢气至压力为3.0~4.0MPa,升温至170~250℃,控制压力为3~5MPa,加氢反应7~20小时,得含有1-四氢萘酮的混合物。
作为优选,所述后处理的具体操作如下:
将所述含有1-四氢萘酮的混合物碱洗,随后精馏得所述1-四氢萘酮。后处理过程中,需要多次碱洗,优选为2~5次。
与现有技术相比,本发明的有益效果为:
本发明的制备方法,采用廉价的1-萘酚与氢气进行加氢反应,通过控制加氢反应温度,有效减少了加氢反应的主要产物种类,降低了目标产物的分离难度。之后根据加氢反应后混合物中各物质的性质,依次采用多次碱洗,最后精馏的方式分离出纯度较高的目标产物1-四氢萘酮。本发明的制备方法,工艺简单,操作方便,加氢反应转化率高,反应过程无废水产生,原料和加工成本低。
附图说明
图1为本发明实施例1中制得的1-四氢萘酮的核磁氢谱图。
具体实施方式
实施例1:
压力釜中,将100克1-萘酚溶解于400ml甲苯中,加入2.5克雷尼镍催化剂,氮气置换3次,然后充氢气到压力3.0MPa,开始升温到235~240℃,然后在压力4.0~4.3MPa下,加氢反应10小时,然后降温到常温,粗品GC检测含量,产物(4)9.883%,产物(1)11.973%,原料5.228%,产物(2)71.768%,然后经过4次碱洗,再精馏得到67%(以1-萘酚摩尔量计算的收率,其他实施例同)的产品1-四氢萘酮,纯度为98.5%,其核磁数据如图1所示。
实施例2:
向压力釜内加入400克1-萘酚和11克雷尼镍催化剂,氮气置换3次,然后充氢气到压力3.0MPa,开始升温到200~205℃,然后在压力3.0~4.0MPa下,加氢反应8小时,然后降温到常温,粗品GC检测含量,产物(4)8.349%,产物(1)7.459%,原料5.082%,产物(2)78.089%,然后经过4次碱洗,再精馏得到72%收率的产品1-四氢萘酮,纯度为98.0%。
实施例3:
压力釜中,将100克1-萘酚溶解于400ml甲苯中,加入1.0克雷尼镍催化剂,氮气置换3次,然后充氢气到压力3.0MPa,开始升温到235~240℃,然后在压力4.0~5.0MPa下,加氢反应20小时,然后降温到常温,粗品GC检测含量,产物(4)9.687%,产物(1)7.221%,原料6.719%,产物(2)75.024%,然后经过4次碱洗,再精馏得到70%收率的产品1-四氢萘酮,纯度为98.3%。
对比例:
100克1-萘酚溶解于400ml甲苯中,加入10克雷尼镍催化剂,氮气置换3次,充入氢气,在压力3.0~3.5MPa,200℃条件下加氢反应7小时,然后降温到常温,粗品GC检测含量,未检测出产物(2)。
由对比例1可知,催化剂加入量过大时,目标产物1-四氢萘酮会进一步转化为其他副产物,无法得到最终的目标产物。
综上所述:1-萘酚加入1-4倍甲苯或者不加溶剂,加入0.01~0.03倍雷尼镍催化剂,在温度200~250℃,在氢气3.0~5.0MPa压力下,反应7~20小时,生成转化率70%~80%的1-四氢萘酮,精馏得到65%~73%收率的1-四氢萘酮。
Claims (7)
1.一种1-四氢萘酮的制备方法,其特征在于,包括:
雷尼镍催化下,反应温度为200~250℃,反应压力为3.0~5.0Mpa,1-萘酚与氢气发生加氢反应,得含有1-四氢萘酮的混合物,后处理得所述1-四氢萘酮;雷尼镍与所述1-萘酚的质量比为(0.01~0.05):1;
所述后处理的具体操作如下:
将所述含有1-四氢萘酮的混合物碱洗,随后精馏得所述1-四氢萘酮。
2.根据权利要求1所述的1-四氢萘酮的制备方法,其特征在于,所述加氢反应在无溶剂状态下进行。
3.根据权利要求1所述的1-四氢萘酮的制备方法,其特征在于,所述加氢反应在有机溶剂中进行。
4.根据权利要求3所述的1-四氢萘酮的制备方法,其特征在于,所述有机溶剂为甲苯和二甲苯中的一种或二者的混合。
5.根据权利要求3所述的1-四氢萘酮的制备方法,其特征在于,所述1-萘酚与所述有机溶剂的质量体积比为(0.25~1)g/ml。
6.根据权利要求1所述的1-四氢萘酮的制备方法,其特征在于,所述加氢反应时间为7~20小时。
7.根据权利要求1所述的1-四氢萘酮的制备方法,其特征在于,雷尼镍与所述1-萘酚的质量比为(0.01~0.03):1。
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