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A new concept for preparing pyrazolidine by the oxidation of 1,3-diaminopropane. Synthesis and formulation of a kinetic model

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Abstract

The present study describes a new way of preparing pyrazolidine by intramolecular Raschig amination using 1,3-diaminopropane and sodium hypochlorite. A global process has been developed, involving the characterization of the reaction mechanisms, kinetic studies and the optimization of the synthesis parameters. The rates were determined as a function of the reagent concentrations, pH and temperature. The overall reaction, of the first order with respect to both reagents, is the result of two successive mechanisms: the first being pH independent, the second accelerated by increasing pH. The bimolecular rate was simulated as a function of hydroxide ion activity. The activation enthalpy and entropy of the molecular process were established at 25 °C. A kinetic model is proposed and then validated by the experimental results. Finally, it was found that the yield of pyrazolidine essentially depends on the ratio p ([1,3-diaminopropane]0/[sodium hypochlorite]0) of the initial molar concentrations and the ratio of the rates k2/k1 (k1: rate of the N,N-dichloro-1,3-diaminopropane formation and k2: rate of N-chloro-1,3 diaminopropane formation).

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Authors and Affiliations

  1. Université Claude Bernard Lyon 1, Laboratoire Hydrazines et Composés Energétiques Polyazotés – UMR 5278, UCBL/CNRS/CNES/Herakles (groupe Safran), 22 Avenue Gaston Berger, 69622, Villeurbanne Cedex, France

    A. El Hajj, A. J. Bougrine, D. M. Le, V. Pasquet & H. Delalu

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  1. A. El Hajj
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  2. A. J. Bougrine
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  3. D. M. Le
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  4. V. Pasquet
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  5. H. Delalu
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Correspondence to V. Pasquet.

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El Hajj, A., Bougrine, A.J., Le, D.M. et al. A new concept for preparing pyrazolidine by the oxidation of 1,3-diaminopropane. Synthesis and formulation of a kinetic model. Reac Kinet Mech Cat 117, 429–446 (2016). https://doi.org/10.1007/s11144-015-0966-5

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  • DOI: https://doi.org/10.1007/s11144-015-0966-5

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