Reaction of Highly Volatile Organic Compounds with Organolithium Species in Flow Microreactor

Abstract

Highly volatile organic compounds (VOCs) with boiling points (bp) around or below room temperature are generally difficult to manipulate precisely in liquid-phase organic reactions although they offer significant atom-economic advantages. We have developed a novel approach using a jacketed syringe pump to enable the formylation of organolithium species in a continuous-flow system under ambient pressure. Methyl formate (bp 32 °C) worked as a formylating agent and was successfully delivered to the continuous operation for over 30 minutes in our microflow system. This methodology was successfully expanded to the application of acetaldehyde (bp 21 °C) and heptafluoropropyl bromide (bp 12 °C).

Key words

volatile organic compounds - organolithium species - flow chemistry - reactive intermediates - device control

Publication History

Received: 06 August 2023

Accepted after revision: 07 September 2023

Accepted Manuscript online:
07 September 2023

Article published online:
30 October 2023

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• 20 General Procedure: Solutions were continuously introduced to the flow microreactor system using syringe pumps (Harvard PHD2000 and TELEDYNE ISCO SyriXus 260x). A flow microreactor system consisting of two T-shaped micromixers (M1 and M2, φ = 250 or 500 μm), two microtube reactors (R1 and R2), and four tube precooling units were used. The flow microreactor system was dipped in a cooling bath₁ (T ₁ °C), and cooling bath₂ (T ₂ °C). After reaching a steady state, the outcoming solution was collected for 30 seconds in a vessel containing 4 mL of sat. aq. NH₄Cl. The yield was determined by GC analysis using undecane as an internal standard.