Computational study of TNT synthesis in solvated nitration reaction systems

Liu, Min-Hsien; Cheng, Ken-Fa; Chen, Cheng; Hong, Yaw‐Shun

doi:10.1002/qua.21925

Cited by 6 publications

(4 citation statements)

References 24 publications

(23 reference statements)

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“…The most direct approach for computing the regioselectivity is to characterize all the stationary points along the PES and to estimate the rate constants from the free energy difference between the rate-determining transition states. A number of studies have used this approach, without fully reproducing the observed isomer distribution [ 7 , 14 – 16 ]. An approximate variant is to use the energy of the corresponding σ-complex structure as an indicator of the transition state energy (the “σ-complex approach”).…”

Section: Introductionmentioning

confidence: 99%

Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach

2017

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The potential energy surfaces in gas phase and in aqueous solution for the nitration of benzene, chlorobenzene, and phenol have been elucidated with density functional theory at the M06-2X/6-311G(d,p) level combined with the polarizable continuum solvent model (PCM). Three reaction intermediates have been identified along both surfaces: the unoriented π-complex (I), the oriented reaction complex (II), and the σ-complex (III). In order to obtain quantitatively reliable results for positional selectivity and for modeling the expulsion of the proton, it is crucial to take solvent effects into consideration. The results are in agreement with Olah’s conclusion from over 40 years ago that the transition state leading to (II) is the rate-determining step in activated cases, while it is the one leading to (III) for deactivated cases. The simplified reactivity approach of using the free energy for the formation of (III) as a model of the rate-determining transition state has previously been shown to be very successful for halogenations, but problematic for nitrations. These observations are rationalized with the geometric and energetic resemblance, and lack of resemblance respectively, between (III) and the corresponding rate determining transition state. At this level of theory, neither the σ-complex (III) nor the reaction complex (II) can be used to accurately model the rate-determining transition state for nitrations.

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Section: Introductionmentioning

confidence: 99%

Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach

2017

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“…Nitration reactions to form C‐N bonds have been widely used for the preparation of nitro compounds in numerous areas of applied research . Owing to the widespread presence of nitro compounds in pharmaceuticals, natural products, organic intermediates, catalysts, and high energy density materials, the application of this process has been exceptionally broad. However, based on the principles of green chemistry, most industrial nitration processes are less environmentally‐friendly because they use nitric acid, nitrates, and nitrous esters as nitrating agents .…”

Section: Introductionmentioning

confidence: 99%

The application of nitrogen oxides in industrial preparations of nitro compounds

2018

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Nitrogen oxides of atomic economy are promising nitrating agents instead of common nitric and sulphuric acids in the industrial preparations of nitro compounds. This review provides recent developments of nitration using nitrogen oxides found in applied research. Novel nitration involving three classes of nitrogen oxides is described for the synthesis of organic intermediates, medicinally relevant compounds, natural products, high energy density materials, and some catalytic materials.

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“…Previously, we performed the successful synthesis and simulation of high‐energy explosives . In this study, we performed theoretical simulations of the newly developed, high‐energy TNTA explosive.…”

Section: Introductionmentioning

confidence: 99%

Comparative theoretical synthesis of high-energy density materials 2,4,6-trinitro-1,3,5-triazine

Cheng

Liu

2014

Int. J. Quantum Chem.

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In this study, the optimal synthetic route for 2,4,6‐trinitro‐1,3,5‐triazine (TNTA) was investigated. The synthesis of TNTA was performed using cyanamide (H2NCN) as a starting material. In the first stage, a radical addition reaction was used to generate melamine, which is the precursor of TNTA. In addition, a gaseous nitration reaction using nitrogen dioxide radicals (•NO2) as the nitration agent was used to gradually induce radical substitutions to convert dicyandiamide (H2NCN)2 to melamine (H2NCN)3. Additional nitration steps lead to triaminocyanide and, ultimately, TNTA. In addition, nitryl cyanide (O2NCN) was also tested as a starting material for radical addition to generate dinitryl cyanide (O2NCN)2, trinitryl cyanide (O2NCN)3, and, finally, TNTA. The activation energy barrier in each of the reaction steps as well as the various synthetic routes were compared to provide insight into the design of more feasible routes for the synthesis of TNTA. © 2014 Wiley Periodicals, Inc.

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Computational study of TNT synthesis in solvated nitration reaction systems

Cited by 6 publications

References 24 publications

Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach

Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach

The application of nitrogen oxides in industrial preparations of nitro compounds

Comparative theoretical synthesis of high-energy density materials 2,4,6-trinitro-1,3,5-triazine

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