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. 2025 Jan 22;16(2):125.
doi: 10.3390/mi16020125.

Modeling the Reaction Process for the Synthesis of Ethyl Chrysanthemate from Ethyl Diazoacetate in a Micro-Flow Platform

Dawei Xin  1 , Yangcheng Lu  1
Affiliations

Modeling the Reaction Process for the Synthesis of Ethyl Chrysanthemate from Ethyl Diazoacetate in a Micro-Flow Platform

Dawei Xin et al. Micromachines (Basel). .

Abstract

Ethyl diazoacetate can react with 2,5-dimethyl-2,4-hexadiene to yield ethyl chrysanthemumate, an important raw material for synthesizing various pesticides. In conventional conditions, this cyclopropanation process suffers from low efficiency and yield due to ethyl diazoacetate. This demands more understanding of the catalytic process from the mechanism and modeling to find a solution. In this work, we set up a micro-flow platform to carefully study the kinetic characteristics of the cyclopropanation reaction of ethyl diazoacetate catalyzed by a complex of copper stearate and phenylhydrazine. Through a reasonable simplification of the reaction network, we established a reaction kinetic model with good prediction capacity within a wide range of operating conditions. It provides a basis for guiding the development of efficient conversion processes and condition optimization.

Keywords: cyclopropanation process; ethyl chrysanthemate; ethyl diazoacetate; kinetic model; reaction mechanism.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis process of ethyl chrysanthemate. (a) Martel route; (b) dimethylhexadiene route.
Scheme 2
Scheme 2
Summarized reaction steps in catalytic cyclopropanation process.
Figure 1
Figure 1
Schematic of (a) the micro-flow platform for the ethyl diazoacetate cyclopropanation experiments and (b) the connection method for 7-way valves.
Figure 2
Figure 2
Kinetic experimental data and model fitting under different olefin excess ratios. Experimental conditions: T = 130 °C; Ccat = 0.02 mmol/L; CEDA = 0.02 mol/L; CDMH = (a) 0.022 mol/L; (b) 0.044 mol/L; and (c) 0.066 mol/L.
Figure 3
Figure 3
Kinetic experimental data and model fitting under different reactant concentrations. Experimental conditions: T = 130 °C; Ccat = 0.02 mmol/L; (a) CEDA = 0.02 mol/L and CDMH = 0.022 mol/L; (b) CEDA = 0.04 mol/L and CDMH = 0.044 mol/L; (c) CEDA = 0.06 mol/L and CDMH = 0.066 mol/L.
Figure 4
Figure 4
Kinetic experimental data and model fitting under different reaction temperatures. Experimental conditions: Ccat = 0.02 mmol/L; CEDA = 0.02 mol/L; CDMH = 0.022 mol/L; T = (a) 110 °C; (b) 120 °C; (c) 130 °C; and (d) 110 °C.
Scheme 3
Scheme 3
A simplified catalytic cyclopropanation reaction network.
Figure 5
Figure 5
Regression correlation of reaction rate constants and temperature.
Figure 6
Figure 6
(a) EC yield of the catalytic cyclopropanation reaction with a copper stearate–phenylhydrazine catalyst varying with temperature and time. (b) The curve of EC yield vs. temperature after a 3 h reaction. Calculation conditions: 60 to 170 °C, Ccat = 0.02 mmol/L, CEDA = 0.02 mol/L, CDMH = 0.02 mol/L. The region of the purple rectangle represents the conditions the kinetic experiments used. The yellow and green circles correspond to two experimental conditions for model validation.
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