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Proceeding Paper

A Facile Method for Assessing the Change in Detonation Properties during Chemical Functionalization: The Case of NH2→NHNO2 and NH2→=N+=N Conversions †

Sergey Bondarchuk
Department of Chemistry and Nanomaterials Science, Institute of Natural and Agrarian Sciences, The Bohdan Khmelnytsky National University of Cherkasy, 18031 Cherkasy, Ukraine
Presented at the 26th International Electronic Conference on Synthetic Organic Chemistry, 15–30 November 2022; Available online:
Chem. Proc. 2022, 12(1), 48;
Published: 14 November 2022


A simple and fast procedure for estimation of the effect of chemical functionalization on the change in detonation properties of energetic materials is reported. The procedure consists of two levels. Computations at Level 1 can be performed with a pocket calculator. At Level 2, quantum-chemical calculations are needed, but these include only three computational tasks: vacuum-isolated molecule relaxation (PBE/DND) → crystal structure prediction (COMPASSII) → crystal cell relaxation (PBE/DND). Thus, we have analyzed transformation of both aromatic and aliphatic amines into the corresponding nitramines and diazo compounds. The calculations at Level 1 indicated that both crystal density (dc) and solid-state enthalpy of formation (ΔHf) are always positive and increase detonation properties, while the calculations at Level 2 revealed the amines that are the most sensitive to such chemical transformation.

1. Introduction

Recently, we have proposed a convenient method for estimation of crystalline density (dc) and solid-state enthalpy of formation (ΔHf) on the basis of empirical formulas of C–H–N–O energetic materials; these were then applied for prediction of their detonation properties [1]. Using this method, we compiled a list of the predicted values of dc, ΔHf, detonation energy (Q), velocity (D) and pressure (P) for all compositions up to C30H30N30O30 [1]. This method appeared to be very useful for predicting the influence of chemical transformation on changes in detonation properties, since one only needs find the interested compound in the table and crudely estimate its potential as an energetic material, or compare its potential with other molecule in the table. Thus, we have recently shown how this method performs for chemical transformation of energetic amines in corresponding triazenes [2] and pentazoles [3].
At the same time, due to a recent trend in the synthesis of nitrogen-rich heterocyclic energetic materials [4,5,6,7], the number of interesting and promising energetic amines demonstrates sustainable growth. Consequently, the area of its possible functionalization plays an increasingly important role. Apart from triazenes and pentazoles, it is interesting to estimate how the detonation properties change upon transformation into the corresponding nitramines and diazo compounds. Both these families of compounds are energetic and well known as conventional explosives [8,9,10]. The specific chemical route leading to these classes of compounds is also known and can be schematically illustrated as follows (Scheme 1) [11,12,13,14,15]:
Thus, in this work, we have applied a two-level scheme to estimate the potential of the aforementioned chemical reactions for enhancing the detonation properties of a number of heterocyclic nitrogen-rich amines.

2. Computational Method

Quantum-chemical calculations in this work were performed using the Materials Studio 2017 suite of programs [16]. Crystal structure predictions were done using ab initio forcefield condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASSII) [17]. The predicted values were then corrected using the previously developed regression model [2,3]:
dtheor = 1.0144 dpred − 0.0706,
where dpred is the uncorrected value obtained using the COMPASSII calculations.
Geometry optimizations of vacuum-isolated molecules and crystals were carried out within all-electron approximation with pure GGA function due to Perdew–Burke–Ernzerhof (PBE) [18], together with a double numerical basis set, DND, as implemented in the DMol3 code [19]. Enthalpies of formation were calculated using the following Equations (2) and (3):
ΔHf,pred = ECiHjNkOl − (iEC + jEH + kEN + lEO),
where ECiHjNkOl is the total energy of the crystal geometry optimization and EX are the corresponding atomic increments [2]. The ΔHf,pred values were then corrected using the following regression model [2]:
ΔHf,theor = 1.1142 ΔHf,pred − 44.657,
Detonation properties were calculated using the Kamlet–Jacobs scheme [20].

3. Results and Discussion

3.1. Calculation at Level 1

The changes in empirical formulas for transformation into nitramines and diazo compounds are expressed in Equations (4) and (5). Taking into account the general method for estimation of ΔHf [1], one can express the constant differences ΔΔHf, which are presented in Equations (6) and (7).
CxHyNzOw → CxHy−1Nz+1Ow+2
CxHyNzOw → CxHy−3Nz+1Ow
ΔΔHf = 1.2845(N + 2O − H) = 3.85 kJ/mol
ΔΔHf = 1.2845(N − 3H) = 214.51 kJ/mol
It is clear that the studied reactions always increase the heat of formation that leads to increased detonation properties. On the other hand, the more important property is crystal density. Taking into account the previously developed equation for dc [1], the same difference Δdc, can be expressed as in Equation (8) and Table 1:
Δ d c = 0.2965 ( a 1 x + a 2 y + a 3 z + a 4 w ) ( V M ( atoms ) ) ( b + V M ( atoms ) )
where VM(atoms) are the previously estimated atomic volumes [1].
As it follows from Equation (8) and Table 1, the expected Δdc are about 0.2 g/cm3 for compositions of typical energetic materials and are always positive, too. Thus, fast calculations at Level 1, which can be performed without involvement of quantum-chemical methods, endorse the transformation of amines into nitramines and diazo compounds.

3.2. Calculations at Level 2

On the basis of calculations at Level 2, we have identified those chemical compositions that are sensitive to the studied transformations and selected the corresponding experimentally available energetic amines from the literature. Chemical structures of the potential products of the amine transformations into nitramines (115) and diazo compounds (1630) are illustrated in Figure 1, and the calculated absolute values of detonation properties and their changes caused upon the transformation are listed in Table 2. As one can see in Table 2, the calculations at both levels demonstrate an increase in detonation properties. At Level 1, the mean absolute and relative differences in Q, D and P values under the formation of nitramines are 166 cal/g (13.8%), 680 m/s (8.7%) and 6.0 GPa (23.2%), respectively. For diazo compounds, these differences for Q, D and P are the following: 266 cal/g (26.2%), 459 m/s (6.5%) and 3.9 GPa (18.7%), respectively. The differences obtained at Level 2 are generally comparable. For example, in the case of the nitramine formation, the Q, D and P values are the following: 323 cal/g (47.9%), 1191 m/s (15.5%) and 10.6 GPa (39.2%), respectively. Finally, for diazo compounds, these differences are the following: 597 cal/g (225.1%), 1041 m/s (20.1%) and 5.1 GPa (46.2%) for Q, D and P, respectively.
The absolute predicted values of D and P indicate that transformation into the nitramines is most effective for the precursor of compound 8 (Figure 1). In this case, one can expect an increase in detonation properties up to 2028 m/s and 13.8 GPa (Table 2). At the same time, for the diazo compounds, a significant gain in detonation properties was observed only for precursors with a very low detonation profile, namely, compounds 19, 20, 24 and 25 (Table 2). The transformation of amines into diazo compounds can even slightly reduce detonation properties, such as in the case of compounds 17 and 18 (Table 2). This is mainly caused by the lower crystal density of the resulting diazo compounds due to the vanishing of intermolecular hydrogen bonds (Figure 1). The only compound that demonstrates a significant rise in detonation properties and has high absolute values is compound 16 (Table 2).

4. Conclusions

Thus, in this article, we have presented an example of using our two-level scheme to evaluate the effectiveness of changes in the detonation properties of energetic amines that have undergone two types of chemical functionalization. Since this family of nitrogen-rich energetic compounds demonstrates intensive growth, it is of current interest to study possible routes for the enhancement of their detonation profiles by means of a simple functionalization. Thus, in this work, we have found that transformation of amines into corresponding nitramines increases their detonation properties by up to 15 and 40% for D and P, as an average. At the same time, transformation into diazo compounds generally has a little effect on highly energetic amines. A significant enhancement is observed only for low-energy density precursors. Nevertheless, in this work, we have revealed the energetic amines whose detonation properties can be easily enhanced via a simple one-pot functionalization. These are the amine precursors of the compounds 8 and 16.


This work was supported by the Ministry of Education and Science of Ukraine, Research Fund (Grant No. 0122U000760).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The author declares no conflict of interest.


  1. Bondarchuk, S.V. Magic of numbers: A guide for preliminary estimation of the detonation performance of C–H–N–O explosives based on empirical formulas. Ind. Eng. Chem. Res. 2021, 60, 1952–1961. [Google Scholar] [CrossRef]
  2. Bondarchuk, S.V. Diazoamination: A simple way to enhance detonation performance of aminoaromatic and aminoheterocyclic energetic materials. FirePhysChem 2021, 1, 97–102. [Google Scholar] [CrossRef]
  3. Bondarchuk, S.V. Structure enhancement of energetic materials: A theoretical study of the arylamines to arylpentazoles transformation. FirePhysChem 2021, 1, 190–197. [Google Scholar] [CrossRef]
  4. Tang, J.; Yang, H.; Cui, Y.; Cheng, G. Nitrogen-rich tricyclic-based energetic materials. Mater. Chem. Front. 2021, 5, 7108–7118. [Google Scholar] [CrossRef]
  5. Wang, L.; Zhai, L.; She, W.; Wang, M.; Zhang, J.; Wang, B. Synthetic strategies toward nitrogen-rich energetic compounds via the reaction characteristics of cyanofurazan/furoxan. Front. Chem. 2022, 10, 871684. [Google Scholar] [CrossRef]
  6. Luo, Y.; Zheng, W.; Wang, X.; Shen, F. Nitrification progress of nitrogen-rich heterocyclic energetic compounds: A review. Molecules 2022, 27, 1465. [Google Scholar] [CrossRef] [PubMed]
  7. Yao, Y.; Adeniyi, A.O. Solid nitrogen and nitrogen-rich compounds as high-energy-density materials. Phys. Status Solidi B 2021, 258, 2000588. [Google Scholar] [CrossRef]
  8. Yang, J.; Wang, G.; Gong, X.; Zhang, J.; Wang, Y.A. High-energy nitramine explosives: A design strategy from linear to cyclic to caged molecules. ACS Omega 2018, 3, 9739–9745. [Google Scholar] [CrossRef] [PubMed]
  9. Green, S.P.; Wheelhouse, K.M.; Payne, A.D.; Hallett, J.P.; Miller, P.W.; Bull, J.A. Thermal stability and explosive hazard assessment of diazo compounds and diazo transfer reagents. Org. Process Res. Dev. 2019, 24, 67–84. [Google Scholar] [CrossRef]
  10. Antonsen, S.; Aursnes, M.; Gallantree-Smith, H.; Dye, C.; Stenstrøm, Y. Safe synthesis of alkylhydroxy and alkylamino nitramines. Molecules 2016, 21, 1738. [Google Scholar] [CrossRef]
  11. Zollinger, H.B. Diazo Chemistry II Aliphatic, Inorganic and Organometallic Compounds; VCH: Weinheim, Germany, 1995; pp. 11–95. [Google Scholar]
  12. Buckle, D.R.; Pinto, I.L. Functions bearing two nitrogens. In Comprehensive Organic Functional Group Transformations; Elsevier: Amsterdam, The Netherlands, 1995; Volume 4, pp. 403–449. [Google Scholar] [CrossRef]
  13. Du, Y.; Zhang, J.; Peng, P.; Su, H.; Li, S.; Pang, S. Synthesis and characterization of three pyrazolate inner diazonium salts: Green, powerful and stable primary explosives. New J. Chem. 2017, 41, 9244–9249. [Google Scholar] [CrossRef]
  14. Klapötke, T.M. New nitrogen-rich high explosives. Struct. Bond. 2007, 125, 85–121. [Google Scholar] [CrossRef]
  15. Dalinger, I.L.; Cherkasova, T.I.; Shevelev, S.A. Synthesis of 4-diazo-3,5-dinitropyrazole and characteristic features of its behaviour towards nucleophiles. Mendeleev Commun. 1997, 7, 58–59. [Google Scholar] [CrossRef]
  16. Materials Studio 2017; Dassault Systèmes BIOVIA: San Diego, CA, USA, 2016.
  17. Sun, H.; Jin, Z.; Yang, C.; Akkermans, R.L.C.; Robertson, S.H.; Spenley, N.A.; Miller, S.; Todd, S.M. COMPASS II: Extended coverage for polymer and drug-like molecule databases. J. Mol. Model. 2016, 22, 47. [Google Scholar] [CrossRef]
  18. Perdew, J.P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868. [Google Scholar] [CrossRef]
  19. Delley, B. From molecules to solids with the DMol3 approach. J. Chem. Phys. 2000, 113, 7756–7764. [Google Scholar] [CrossRef]
  20. Kamlet, M.J.; Jacobs, S.J. Chemistry of detonations. I. A simple method for calculating detonation properties of C–H–N–O explosives. J. Chem. Phys. 1968, 48, 23–35. [Google Scholar] [CrossRef]
  21. Gao, H.; Zhang, Q.; Shreeve, J.M. Fused heterocycle-based energetic materials (2012–2019). J. Mater. Chem. A 2020, 8, 4193–4216. [Google Scholar] [CrossRef]
  22. Gao, H.; Shreeve, J.M. Azole-based energetic salts. Chem. Rev. 2011, 111, 7377–7436. [Google Scholar] [CrossRef]
  23. Yin, P.; Shreeve, J.M. Nitrogen-rich azoles as high density energy materials. Adv. Heterocycl. Chem. 2017, 121, 89–131. [Google Scholar] [CrossRef]
  24. Bennion, J.C.; McBain, A.; Son, S.F.; Matzger, A.J. Design and synthesis of a series of nitrogen-rich energetic cocrystals of 5,5′-dinitro-2H,2h′-3,3′-bi-1,2,4-triazole (DNBT). Crystal Growth Des. 2015, 15, 2545–2549. [Google Scholar] [CrossRef]
  25. Yount, J.; Zeller, M.; Byrd, E.F.C.; Piercey, D.G. 4,4′-Dinitrimino-5,5′-diamino-3,3′-azo-bis-1,2,4-triazole: A high-performing zwitterionic energetic material. Inorg. Chem. 2021, 60, 16204–16212. [Google Scholar] [CrossRef] [PubMed]
  26. Chinnam, A.K.; Staples, R.J.; Shreeve, J.M. Nucleophilic catalyzed structural binary cleavage of a fused [5,5]-bicyclic compound. Org. Lett. 2021, 23, 9408–9412. [Google Scholar] [CrossRef]
  27. Song, H.; Li, B.; Gao, X.; Shan, F.; Ma, X.; Tian, X.; Chen, X. Thermodynamics and catalytic properties of two novel energetic complexes based on 3-amino-1,2,4-triazole-5-carboxylic acid. ACS Omega 2022, 7, 3024–3029. [Google Scholar] [CrossRef] [PubMed]
  28. Jia, Y.; Ma, Q.; Zhang, Z.-Q.; Geng, W.; Huang, J.; Yang, W.; Fan, G.-J.; Wang, S. Energetic 1H-imidazo[4,5-d]pyridazine-2,4,7-triamine: A novel nitrogen-rich fused heterocyclic cation with high density. Cryst. Growth Des. 2020, 20, 3406–3412. [Google Scholar] [CrossRef]
  29. Tang, Y.; He, C.; Mitchell, L.A.; Parrish, D.A.; Shreeve, J.M. Energetic compounds consisting of 1,2,5- and 1,3,4-oxadiazole rings. J. Mater. Chem. A 2015, 3, 23143–23148. [Google Scholar] [CrossRef]
  30. Mathpati, R.S.; Yadav, A.K.; Ghule, V.D.; Dharavath, S. Potential energetic salts of 5,5′-methylenedi(4H-1,2,4-triazole-3,4-diamine) cation: Synthesis, characterization and detonation performance. Energ. Mater. Front. 2022, 3, 90–96. [Google Scholar] [CrossRef]
  31. Tang, Y.; An, Z.; Chinnam, A.K.; Staples, R.J.; Shreeve, J.M. Very thermostable energetic materials based on a fused-triazole: 3,6-diamino-1H-[1,2,4]triazolo[4,3-b][1,2,4]triazole. New J. Chem. 2021, 45, 85–91. [Google Scholar] [CrossRef]
Scheme 1. Chemical routes from amines to diazo compounds (left) and nitramines (right).
Scheme 1. Chemical routes from amines to diazo compounds (left) and nitramines (right).
Chemproc 12 00048 sch001
Figure 1. Chemical structures of the potential nitramines (115) and diazo compounds (1630).
Figure 1. Chemical structures of the potential nitramines (115) and diazo compounds (1630).
Chemproc 12 00048 g001
Table 1. Coefficients for nitramines and diazo compounds used in Equation (8).
Table 1. Coefficients for nitramines and diazo compounds used in Equation (8).
Diazo compounds−1939−553−16591302−2
Table 2. The calculated detonation properties (Q in cal/g, D in m/s and P in GPa) obtained at Levels 1 and 2, and the corresponding absolute differences with ones calculated for the amine precursors.
Table 2. The calculated detonation properties (Q in cal/g, D in m/s and P in GPa) obtained at Levels 1 and 2, and the corresponding absolute differences with ones calculated for the amine precursors.
EntryRef.Level 1Level 2
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Bondarchuk, S. A Facile Method for Assessing the Change in Detonation Properties during Chemical Functionalization: The Case of NH2→NHNO2 and NH2→=N+=N Conversions. Chem. Proc. 2022, 12, 48.

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Bondarchuk S. A Facile Method for Assessing the Change in Detonation Properties during Chemical Functionalization: The Case of NH2→NHNO2 and NH2→=N+=N Conversions. Chemistry Proceedings. 2022; 12(1):48.

Chicago/Turabian Style

Bondarchuk, Sergey. 2022. "A Facile Method for Assessing the Change in Detonation Properties during Chemical Functionalization: The Case of NH2→NHNO2 and NH2→=N+=N Conversions" Chemistry Proceedings 12, no. 1: 48.

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