Continuous-flow synthesis of prenyl chloride on-demand through surface-mediated hydrochlorination

IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Hang Zhao, Xiao Xiao, Runqi Hao, Dan Chen, Jiawei Ke, Minjie Liu, Li Wan, Fener Chen
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引用次数: 0

Abstract

1-Chloro-3-methyl-2-butene is an important synthetic precursor or alkylating agent in the preparation of various bioactive chemicals and essential nutrients for human beings. A flow surface-mediated HCl in situ generation and subsequent hydrochlorination of isoprene were realized in the PTFE tubing reactor and the packed-bed reactor separately. Up to 86% isolated yield of 1-chloro-3-methyl-2-butene was achieved in the packed-bed reactor by performing the flow hydrochlorination at -15 °C within a 15 min residence time in the presence of 0.5 equiv. SOCl2. The in-line recycling and regenerating of solid proton donor Al2O3 were accomplished via simple washing with DCM and MeOH in sequence, the activity of Al2O3 filled in the packed-bed reactor maintain consistent on the isolated yield of 1-chloro-3-methyl-2-butene after ten times consecutive reutilization. The flow platform consisting of two parallel packed-bed reactors were assembled for the continuous synthesis of desired 1-chloro-3-methyl-2-butene without interruption through delicate coordinating opening direction of a series of three-way valves. Long-term stability and reliability were demonstrated by continuous running the designed cyclic rotation system for 10 h, the targeted hydrochlorination product was furnished in 91–93% yield.

Graphical abstract

Continuous-flow synthesis of prenyl chloride was enabled by cross-sequential utilization strategy using two parallel packed-bed reactors and precise alternating a series of three-way valves opening direction.

通过表面介导的氢氯化反应按需连续流合成戊烯酰氯
1-氯-3-甲基-2-丁烯是制备各种生物活性化学品和人体必需营养素的重要合成前体或烷基化剂。在聚四氟乙烯管反应器和填充床反应器中分别实现了流动表面介导的原位生成HCl和随后的异戊二烯加氢氯化反应。在填充床反应器中,在-15°C条件下,在0.5等量SOCl2存在下,在15分钟的停留时间内进行流动加氢氯化,分离得到1-氯-3-甲基-2-丁烯的收率可达86%。通过DCM和MeOH的顺序简单洗涤,实现了固体质子供体Al2O3的在线回收再生,填充床反应器中Al2O3的活性与连续重复利用10次后1-氯-3-甲基-2-丁烯的分离产率保持一致。由两个平行填料床反应器组成的流动平台,通过一系列三通阀的精细协调开启方向,连续合成所需的1-氯-3-甲基-2-丁烯。设计的循环循环系统连续运行10 h,证明了该系统的长期稳定性和可靠性,目标氯化氢产物的收率为91 ~ 93%。摘要采用两个平行填料床反应器和一系列三通阀的精确交替开启方向,采用交叉顺序利用策略,实现了丙烯酰氯的连续流合成。
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来源期刊
Journal of Flow Chemistry
Journal of Flow Chemistry CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
6.40
自引率
3.70%
发文量
29
审稿时长
>12 weeks
期刊介绍: The main focus of the journal is flow chemistry in inorganic, organic, analytical and process chemistry in the academic research as well as in applied research and development in the pharmaceutical, agrochemical, fine-chemical, petro- chemical, fragrance industry.
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