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Theoretical investigation of reaction mechanisms of alkaline hydrolysis of 2,3,6-trinitro-β-d-glucopyranose as a monomer of nitrocellulose

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Abstract

The 2,3,6-trinitro-β-d-glucopyranose as a monomer of nitrocellulose in the 4C1 chair conformation was selected for the alkaline hydrolysis of nitrocellulose within SN2 framework in the gas phase and in the bulk water solution. Both the direct and angular attacks of OH− in the hydrolysis reactions were considered. Geometries were optimized at the B3LYP/6-311G(d,p) level both in the gas phase and in bulk water solution. Effect of bulk water solution was modeled using the PCM approach. Nature of potential energy surfaces of the local minima and transition states was ascertained through harmonic vibrational frequency analysis. Intrinsic reaction coordinate calculations were also performed to validate the computed transition state structures. Effect of electron correlation on computed energies was considered at the MP2/cc-pVTZ//B3LYP/6-311G(d,p) level. It was found that the angular attack of OH− in the hydrolysis reaction will require significantly larger activation energy than the direct attack. Computed transition states correspond to the structure where the presence of hydrogen bonds between the OH− and various sites of nitrocellulose was the necessary stabilizing factor. The ring breaking through the C–O ring bond was not found to be the first step in the alkaline hydrolysis reactions. It was predicted that alkaline hydrolysis would be driven by the addition–elimination (substitution) reaction starting at the C3 site and will progress in the C2 → C6 direction. Entropy of system in water solution will have profound effect on alkaline hydrolysis reaction of nitrocellulose.

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Acknowledgments

The use of trade, product, or firm names in this report is for descriptive purposes only and does not imply endorsement by the U.S. Government. The tests described and the resulting data presented herein, unless otherwise noted, were obtained from research conducted under the Environmental Quality Technology Program of the United States Army Corps of Engineers and the Environmental Security Technology Certification Program of the Department of Defense by the USAERDC. Permission was granted by the Chief of Engineers to publish this information. The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents. The authors thank Dr. Andrea Scott and Dr. Anthony Bednar of the USACE for their editorial comments.

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  1. US Army Engineer Research and Development Center, Environmental Laboratory, 3909 Halls Ferry Road, Vicksburg, MS, 39180-6199, USA

    Manoj K. Shukla & Frances Hill

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  1. Manoj K. Shukla
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  2. Frances Hill
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Correspondence to Manoj K. Shukla.

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Shukla, M.K., Hill, F. Theoretical investigation of reaction mechanisms of alkaline hydrolysis of 2,3,6-trinitro-β-d-glucopyranose as a monomer of nitrocellulose. Struct Chem 23, 1905–1920 (2012). https://doi.org/10.1007/s11224-012-9977-2

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  • DOI: https://doi.org/10.1007/s11224-012-9977-2

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