CN111205189A - 一种微通道反应器制备邻硝基溴苄的方法 - Google Patents
一种微通道反应器制备邻硝基溴苄的方法 Download PDFInfo
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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Abstract
本发明公开了一种微通道反应器制备邻硝基溴苄的方法,该制备方法以邻硝基甲苯为原料,溴素为溴源,在催化剂的引发下,通过微通道反应器反应生成邻硝基溴苄,本发明具有生产效率高,纯度高,操作简便,安全等优点,适合工业化生产。
Description
技术领域
本发明属于化学合成技术领域,具体而言,涉及一种微通道反应器制备邻硝基溴苄的方法。
背景技术
吡唑醚菌酯Pyraclostrobin,又名唑菌胺酯,是由德国巴斯夫公司于1993年发现的一种兼具吡唑结构的甲氧丙烯酸甲酯类广谱杀菌剂。2002年上市。它高效、广谱、低毒,而且对环境安全、友好。至今,吡唑醚菌酯单剂和许多混剂已在60多个国家的150多种作物上登记。该有效成分对谷物、柑橘、棉花、葡萄、香蕉、花生、大豆、甜菜、蔬菜、向日葵和草坪的多种病原菌有效。也可用于种子处理。
邻硝基溴苄是合成吡唑醚菌酯的重要中间体,合成方法有多种,主要是由邻硝基甲苯通过溴化得到。在传统的溴化工艺中是通过高温条件下滴加溴素进行溴化反应[周增勇.4-硝基苄基溴的光照合成方法探索[J].染料与染色,2009,46(5):44-45.],该反应条件选择性差,收率低,反应过程中伴有严重的废气污染,不适于工业化生产。也有文献报道用N-溴代丁二酰亚胺(NBS)作溴源,如Jitendra Kumar Mishra,et al,Bioorganic&Medicinal Chemistry Letters(2007),17,(5),1326-1331、专利CN 104592117A,这两篇文献中报道的溴化收率分别为69%和58.8%,收率均不高,且溴化剂NBS较昂贵。还有文献报道用氢溴酸与双氧水作溴源,如专利CN 108069860 A、专利CN 103641722,这两篇专利中报道的溴化收率分别为86%和83%,收率较高,但分别用到了有机溶剂二氯甲烷和,石油醚,生产成本高,环境污染大。
发明内容
本发明的目的在于解决现阶段生产邻硝基溴苄过程中,收率低、原料昂贵,周期长、废水排放较多等问题。
本发明提供了一种微通道反应器制备邻硝基溴苄的方法,该制备方法以邻硝基甲苯为原料,溴素为溴源,在催化剂的引发下连续通过微通道反应器生成邻硝基溴苄,本发明具有高效、简便、可连续生产等优点。
反应方程式如下:
一种微通道反应器制备邻硝基溴苄的方法,步骤如下:
步骤1,将邻硝基甲苯与催化剂混合由计量泵经进样口1注入到第一片微通道反应器内,得到混合液;
步骤2,同步将溴素由计量泵经进样口2注入到第一片微通道反应器内,与步骤1的混合液混合,控制反应器温度60~130℃,得到混合料液;
步骤3,将步骤2得到的混合料液继续通过微通道反应器的反应片,得到反应液;
步骤4,将步骤3所得的反应液导出到冷水中冷却淬灭反应;
步骤5,将步骤4所得的反应液冷却至5~15℃,保温放置3~4h析晶,抽滤得到邻硝基溴苄。
其中,步骤1中所述的催化剂为偶氮二异丁腈或过氧化苯甲酰。
步骤1中所述的邻硝基甲苯与催化剂的质量比为1:(0.02~0.08)。
步骤1中所述的进料流量为5~30g/min。
步骤2中所述的溴素进料流量为5.88~17.65g/min。
步骤3中所述的反应片温度为60~120℃,所述的反应片的数量为7~10片。
步骤4中所述的淬灭温度为5~50℃。
与现有技术相比,本发明的优点是:
1.本发明提供的制备方法以邻硝基甲苯、溴素为原料,在催化剂的引发下,通过控制原料配比、流量以及反应温度,反应液通过微通道反应器,整个反应的时间在几十秒至几分钟内完成,大大缩短了反应时间;
2.本发明提供的制备方法,反应器内的反应液只有十几至几十毫升,即使发生泄露也不会产生严重危害,安全系数高;
3.本发明提供的制备方法操作简单,转化效率高在90~95%之间,二溴代副产物少,纯度高,在99%以上;
4.本发明采用的设备体积小、产量高,在扩大生产时不再需要对反应器进行尺度放大,只需并行增加微反应器的数量,适合工业大生产。
附图说明
图1是本发明的制备工艺流程图;
图2是本发明制备邻硝基溴苄的装置实图。
具体实施方式
下面通过具体实施例对本发明作进一步详细介绍。有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员根据上述发明内容所做出的一些非本质的改进和调整,仍属于本发明的保护范围。
以下实施例的制备工艺流程如图1所示。
以下实施例采用山东微井化工科技股份有限公司生产的微通道反应器,装置实图如图2所示。
实施例1
1)将邻硝基甲苯与偶氮二异丁腈以质量比1:0.02混合溶清后,用计量泵以5g/min的流量经进样口1注入第一片反应片,得到混合液;
2)同步将溴素用计量泵以5.88g/min的流量经进样口2注入第一片反应片,与1)得到的混合液混合,控制反应器温度为90℃,得到混合料液;
3)将2)得到的混合料液连续通过7片串联的反应片,得到反应液;
4)将3)得到的反应液通入到5℃的冷水中淬灭,接料10min;
5)将4)所得料液保温5℃,放置3h,抽滤,干燥后称量得75.8g,收率为96%,液相测得含量99.22%。
实施例2
1)将邻硝基甲苯与偶氮二异丁腈以质量比1:0.04混合溶清后,用计量泵以10g/min的流量经进样口1注入第一片反应片,得到混合液;
2)同步将溴素用计量泵以11.76g/min的流量经进样口2注入第一片反应片,与1)得到的混合液混合,控制反应器温度为100℃,得到混合料液;
3)将2)得到的混合料液连续通过8片串联的反应片,得到反应液;
4)将3)得到的反应液通入到10℃的冷水中淬灭,接料5min;
5)将4)所得料液保温10℃,放置3h,抽滤,干燥后称量得73.4g,收率为92.86%,液相测得含量99.18%。
实施例3
1)将邻硝基甲苯与偶氮二异丁腈以质量比1:0.06混合溶清后,用计量泵以15g/min的流量经进样口1注入第一片反应片,得到混合液;
2)同步将溴素用计量泵以17.65g/min的流量经进样口2注入第一片反应片,与1)得到的混合液混合,控制反应器温度为110℃,得到混合料液;
3)将2)得到的混合料液连续通过10片串联的反应片,得到反应液;
4)将3)得到的反应液通入到25℃的冷水中淬灭,接料3min;
5)将4)所得料液保温10℃,放置4h,抽滤,干燥后称量得67.1g,收率为94.2%,液相测得含量99.11%。
对比例1
以专利CN 108069860 A的制备方案,称取邻硝基甲苯6.9g溶于130g二氯甲烷中,向该体系中依次加入40%HBr溶液13.2g、偶氮二异丁腈0.8g,无水氯化铁0.8g,搅拌加热至回流,以1滴/min滴加30%过氧化氢溶液7.37g,搅拌回流反应2h,冷却至室温,分离出有机相,所述有机相即为邻硝基溴苄。HPLC检测,收率为86.3%,纯度89.21%。
对比例2
以专利CN 103641722的制备方案,在100ml三口烧瓶中,加入水25g、邻硝基甲苯10g、PEG600 0.2g、质量浓度为48%的HBr 11g,偶氮二异丁腈1g,在50~55℃下,滴加质量浓度为30%的双氧水8g,1h左右滴完后,在此温度下保温反应6h,直至红色褪尽,分去上层水层,下层料层用5%亚硫酸钠洗涤后,再用水洗,加入10ml石油醚,搅拌升温溶解,溶解后,将石油醚溶液降至室温,溶液分层,下层为邻硝基甲苯原料,将上层石油醚溶液直接放入冰箱中冷藏静置后,瓶底析出白色晶体,抽滤并用冷的石油醚进行淋洗,得邻白色硝基苄溴固体,收率为80.2%,纯度80.52%。
从实施例1~3与对比例1~2的结果可以看出,本发明比现阶段邻硝基溴苄生产方法收率高,纯度大,且副产物少。
Claims (7)
1.一种微通道反应器制备邻硝基溴苄的方法,其特征在于,步骤如下:
步骤1,将邻硝基甲苯与催化剂混合由计量泵经进样口1注入到第一片微通道反应器内,得到混合液;
步骤2,同步将溴素由计量泵经进样口2注入到第一片微通道反应器内,与步骤1的混合液混合,控制反应器温度60~130℃,得到混合料液;
步骤3,将步骤2得到的混合料液继续通过微通道反应器的反应片,得到反应液;
步骤4,将步骤3所得的反应液导出到冷水中冷却淬灭反应;
步骤5,将步骤4的反应液冷却至5~15℃,保温放置3~4h析晶,抽滤得到邻硝基溴苄。
2.根据权利要求1所述的一种微通道反应器制备邻硝基溴苄的方法,其特征在于,所述的步骤1中所述的催化剂为偶氮二异丁腈或过氧化苯甲酰。
3.根据权利要求1所述的一种微通道反应器制备邻硝基溴苄的方法,其特征在于,所述的步骤1中所述的邻硝基甲苯与催化剂的质量比为1:(0.02~0.08)。
4.根据权利要求1所述的一种微通道反应器制备邻硝基溴苄的方法,其特征在于,所述的步骤1中所述的进料流量5~30g/min。
5.根据权利要求1所述的一种微通道反应器制备邻硝基溴苄的方法,其特征在于,所述的步骤2中所述的溴素进料流量为5.88~17.65g/min。
6.根据权利要求1所述的一种微通道反应器制备邻硝基溴苄的方法,其特征在于,所述的步骤3中所述的反应片温度为60~120℃,所述的反应片的数量为7~10片。
7.根据权利要求1所述的一种微通道反应器制备邻硝基溴苄的方法,其特征在于,所述的步骤4中所述的淬灭温度为5~50℃。
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