Computational optimum conditions for FOX-7 synthesis – A comparative synthesis route

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

doi:10.1016/j.theochem.2010.06.026

Cited by 6 publications

(2 citation statements)

References 27 publications

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“…It has a density of 1.885 g·cm –3 , a heat of formation of −133.7 kJ·mol –1 , the same insensitivity to TATB (1,3,5-triamino-2,4,6-trinitrobenzene) and a similar energy density as those of RDX (1,3,5-trinitroperhydro-1,3,5-triazine) and HMX (cyclotetramethylene tetranitramine). , Since first being synthesized in 1998, FOX-7 has received much attention and been considered as the main component to be used in insensitive ammunitions and solid propellants. Many research studies have been carried out on the synthesis, mechanism, molecule structure, thermal behavior, detonation performance, and application of FOX-7. − FOX-7 is a representative “push–pull” nitro-enamine compound, which possesses a highly polarized carbon–carbon double bond with positive and negative charges being stabilized by the amino group and nitro group, respectively. ,, The positive end of the carbon–carbon double bond can be attacked by nucleophilic reagents to synthesize new singly substituted derivatives or disubstituted closed-loop derivatives. ,− Five disubstituted closed-loop derivatives of FOX-7 (Scheme ) were synthesized by our group, and their structures and some properties were reported in succession. − …”

Section: Introductionmentioning

confidence: 99%

Studies on Thermodynamic Properties of FOX-7 and Its Five Closed-Loop Derivatives

Sun¹,

Xu²,

Z³

et al. 2015

J. Chem. Eng. Data

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Combustion heats of FOX-7 and its five closed-loop derivatives were determined and the standard molar enthalpies of formation (Δ f H°m) were obtained. The sequence of combustion heat for the six compounds is DNDH > MDNZ > DNDX > DNDZ > DDNI > FOX-7. Combustion heat tends to rise with the increase of the number of C atoms in the molecule. Specific heat capacities were measured, and the standard molar heat capacities of the six compounds are (176.59, 205.41, 207.76, 218.89, 217.76, and 215.40) J·mol −1 ·K −1 , respectively. The specific heat capacity presents an opposite change rule with combustion heat. To the isomers and the introduction of hydroxyl group, the change rule is the same. Moreover, the introduction of hydroxyl group can markedly decrease the combustion heat and specific heat capacity.

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Section: Introductionmentioning

confidence: 99%

Studies on Thermodynamic Properties of FOX-7 and Its Five Closed-Loop Derivatives

Sun¹,

Xu²,

Z³

et al. 2015

J. Chem. Eng. Data

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“…Besides, experimental research on high-energy explosives is not only risky, but requires time and financial commitments. We were motivated, based upon past experience, [15][16][17][18][19] to conduct various reactions and obtain results through theoretical computation. Furthermore, quantum chemical theory calculation was used to analyze the kinetic energy barriers and to identify a more beneficial route for the reaction.…”

Section: Introductionmentioning

confidence: 99%

A Computational Study of Reaction Routes of 1,3,3‐trinitroazetidine (TNAZ) Synthesis

Liu

Cheng

Yen

2015

J Chinese Chemical Soc

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This study performs simulation modeling of the synthesis of 1,3,3-trinitro azetidine (TNAZ), a high-energy compound. Based on the experimental nitromethane and 1,3-dihalo-2-propanol raw material methods in the latest literature, we suggest reasonable reaction mechanisms. Using quantum mechanical theory, i.e., electronic density functional theory (DFT) B3LYP/6-31G(d,p) in the Gaussian 09 program, we have completed optimization work for all species in related reaction stages and obtained energy barrier data, which are used to identify the most feasible reaction pathways. Nitromethane has been used to react with formaldehyde through an ionic-type transition to produce 2,2-dinitro-1,3-propandiol, followed by reaction with hydrogen bromide to produce 1,3-dibromo-2,2-dinitro propane, then further react with a tertiary amine to produce 1-tertiary amino-3,3-dinitro azetidine, and subsequently nitrate to obtain TNAZ. Substituent effects of some atomic groups have been found during synthesis modeling, and a total activation energy of 1386.6 kJ/mol needs to be conquered in order to complete the reaction. Furthermore, from synthesis modeling using the 1,3-dihalo-2-propanol raw material method, the suggested reaction routes could be bromination of glycerol to 1,3-dibromo-2-propanol, followed by reaction with nitromethane to undergo amination, and further cyclization, oxidation, oximization, and nitration in sequence to produce the target product TNAZ. An overall 1163.5 kJ/mol energy barrier needs to be overcome in this part of the computation.

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Adsorption and Decomposition Mechanism of 1,1‐Diamino‐2,2‐dinitroethylene on Al(111) Surface by Periodic DFT Calculations

Zhao³

et al. 2012

Chin. J. Chem.

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The adsorption of 1,1-diamino-2,2-dinitroethylene (FOX-7) molecule on the Al(111) surface was investigated by the generalized gradient approximation (GGA) of density functional theory (DFT). The calculations employ a supercell (4×4×2) slab model and three-dimensional periodic boundary conditions. The strong attractive forces between oxygen and aluminum atoms induce the N-O bond breaking of the FOX-7. Subsequently, the dissociated oxygen atoms and radical fragment of FOX-7 oxidize the Al surface. The largest adsorption energy is -940.5 kJ/mol. Most of charge transfer is 3.31e from the Al surface to the fragment of FOX-7 molecule. We also investigated the adsorption and decomposition mechanism of FOX-7 molecule on the Al(111) surface. The activation energy for the dissociation steps of P2 configuration is as large as 428.8 kJ/mol, while activation energies of other configurations are much smaller, in range of 2.4 to 147.7 kJ/mol.

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Computational optimum conditions for FOX-7 synthesis – A comparative synthesis route

Cited by 6 publications

References 27 publications

Studies on Thermodynamic Properties of FOX-7 and Its Five Closed-Loop Derivatives

Studies on Thermodynamic Properties of FOX-7 and Its Five Closed-Loop Derivatives

A Computational Study of Reaction Routes of 1,3,3‐trinitroazetidine (TNAZ) Synthesis

Adsorption and Decomposition Mechanism of 1,1‐Diamino‐2,2‐dinitroethylene on Al(111) Surface by Periodic DFT Calculations

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