ARL-TN-0693 ● SEP 2015

US Army Research Laboratory

Theoretical Prediction of the Heats of 

Formation, Densities and Relative Sensitivities, 

and/or Synthetic Approaches Toward the 

Synthesis of High Energy Dense Materials 

(HEDMs): 3,5-Dinitro-1,3,5-Oxadiazinane, 

Bis-Adjacent RDX, Bis-Adjacent HMX, 4,4',6,6'-

Tetranitro-1,1'-Bis(N-oxide)-5,5',6,6'-4H,4'H5,5'-Bisimidazo Oxadiazole, and the OpenCage Derivative of CL-20

by Edward FC Byrd and Jesse J Sabatini

Approved for public release; distribution is unlimited.
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Army position unless so designated by other authorized documents.

Citation of manufacturer’s or trade names does not constitute an official 

endorsement or approval of the use thereof.

Destroy this report when it is no longer needed. Do not return it to the originator.
ARL-TN-0693 ● SEP 2015

US Army Research Laboratory

Theoretical Prediction of the Heats of 

Formation, Densities and Relative Sensitivities, 

and/or Synthetic Approaches Toward the 

Synthesis of High Energy Dense Materials 

(HEDMs): 3,5-Dinitro-1,3,5-Oxadiazinane, 

Bis-Adjacent RDX, Bis-Adjacent HMX, 4,4',6,6'-

Tetranitro-1,1'-Bis(N-oxide)-5,5',6,6'-4H,4'H5,5'-Bisimidazo Oxadiazole, and the OpenCage Derivative of CL-20

by Edward FC Byrd and Jesse J Sabatini

Weapons and Materials Research Directorate, ARL

Approved for public release; distribution is unlimited.
ii

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1. REPORT DATE (DD-MM-YYYY)

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3. DATES COVERED (From - To)

January 2015–March 2015

4. TITLE AND SUBTITLE

Theoretical Prediction of the Heats of Formation, Densities and Relative 

Sensitivities, and/or Synthetic Approaches Toward the Synthesis of High 

Energy Dense Materials (HEDMs): 3,5-Dinitro-1,3,5-Oxadiazinane, 

Bis-Adjacent RDX, Bis-Adjacent HMX, 4,4',6,6'-Tetranitro-1,1'-Bis(N-oxide)-

5,5',6,6'-4H,4'H-5,5'-Bisimidazo Oxadiazole, and the Open-Cage Derivative of 

CL-20

5a. CONTRACT NUMBER

5b. GRANT NUMBER

5c. PROGRAM ELEMENT NUMBER

6. AUTHOR(S)

Edward FC Byrd and Jesse J Sabatini

5d. PROJECT NUMBER

5e. TASK NUMBER

5f. WORK UNIT NUMBER

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)

US Army Research Laboratory

ATTN: RDRL-WML-B

Aberdeen Proving Ground, MD 21005

8. PERFORMING ORGANIZATION REPORT NUMBER

ARL-TN-0693

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR'S ACRONYM(S)

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12. DISTRIBUTION/AVAILABILITY STATEMENT

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13. SUPPLEMENTARY NOTES

14. ABSTRACT

Using the US Army Research Laboratory (ARL)-developed series of scripts, written to dramatically simplify the computation 

of crystalline density and heat of formation, we evaluated the performance properties for 5 notional energetic materials: 3,5-

dinitro-1,3,5-oxadiazinane, bis-adjacent RDX, bis-adjacent HMX, 4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-

bisimidazo oxadiazole, and the open-cage derivative of CL-20. Additionally, a qualitative estimation of the impact 

sensitivities has been calculated. This technical note outlines the procedures used to generate this information, as well as 

Cheetah calculations using the predicted crystalline densities and heats of formation. Synthetic efforts toward synthesizing 

3,5-dinitro-1,3,5-oxadiazinane, bis-adjacent RDX, and 4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo 

oxadiazole are described, as well as potential synthetic pathways toward synthesizing, bis-adjacent HMX and the open-cage 

derivative of CL-20.

15. SUBJECT TERMS

computational toolbox, script, crystalline density, heat of formation, impact sensitivity, synthesis, energetic materials

16. SECURITY CLASSIFICATION OF:

17. LIMITATION

OF ABSTRACT

UU

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OF PAGES

26

19a. NAME OF RESPONSIBLE PERSON

Edward FC Byrd

a. REPORT

Unclassified

b. ABSTRACT

Unclassified

c. THIS PAGE

Unclassified

19b. TELEPHONE NUMBER (Include area code)

410-306-0729
iii

Contents

List of Figures iv

List of Tables iv

Acknowledgments v

1. Introduction 1

2. Results and Discussion 1

3. Conclusions 14

4. References 15

List of Symbols, Abbreviations, and Acronyms 17

Distribution List 18
iv

List of Figures

Fig. 1 Optimized structures a) 1, b) 2, c) 3, d) 4, and e) 5 ...............................2

Fig. 2 Electrostatic potential map of 1, a) with and b) without molecule 

overlay....................................................................................................4

Fig. 3 Electrostatic potential map of 2, a) with and b) without molecule 

overlay....................................................................................................5

Fig. 4 Electrostatic potential map of 3, a) with and b) without molecule 

overlay....................................................................................................6

Fig. 5 Electrostatic potential map of 4, a) with and b) without molecule 

overlay....................................................................................................7

Fig. 6 Electrostatic potential map of 5, a) with and b) without molecule 

overlay....................................................................................................8

Fig. 7 3,5-dinitro-1,3,5-oxadiazinane (1).........................................................9

Fig. 8 Bis-adjacent RDX (2)...........................................................................10

Fig. 9 Bis-Adjacent HMX (3).........................................................................12

Fig. 10 4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo 

oxadiazole (4).......................................................................................12

Fig. 11 Open-chain CL-20 (5)..........................................................................13

List of Tables

Table 1 Computed heats of formation and crystalline densities for 3,5-dinitro1,3,5-oxadiazinane (1), bis-adjacent RDX (2), bis-adjacent HMX (3), 

4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo 

oxadiazole (4), and the open-cage derivative of CL-20 (5)...................3

Table 2 Cheetah predicted properties for 3,5-dinitro-1,3,5-oxadiazinane (1), 

bis-adjacent RDX (2), bis-adjacent HMX (3), 4,4',6,6'-tetranitro-1,1'-

bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo oxadiazole (4), and the 

open-cage derivative of CL-20 (5).........................................................9
v

Acknowledgments

Dr Betsy Rice and Jennifer J Hare are acknowledged for their efforts in the original 

coding of the neutral heat of formation and EDAT tools, respectively. Dr Anthony 

Yau is acknowledged for his work in revising the EDAT code. Dr James Ianni

(Applications Engineer with Lockheed-Martin, Contractor to the US Army 

Research Laboratory Department of Defense [DOD] Supercomputing Resource 

Center [ARL DSRC]) is acknowledged for his gsubmit script, initially written for 

the ARL DSRC. Dr Betsy Rice is acknowledged for running the Cheetah 

calculations. All computations were performed at the ARL DSRC, Aberdeen 

Proving Ground (APG), Maryland.
vi

INTENTIONALLY LEFT BLANK.
1

1. Introduction

US Army Research Laboratory (ARL) researchers have achieved robust theoretical 

models capable of predicting performance properties, such as heats of 

formation,

1,2 densities,3,4 and impact sensitivity5 of energetic materials (EMs) and 

have begun growing advanced synthesis capabilities to realize notional materials. 

This dual capability allowssynthetic and formulation chemists to safely and quickly 

screen candidate materials to focus efforts only on the most promising compounds. 

For an in depth explanation of the different theoretical methods employed herein, 

please refer to previous works.6,7 This technical note will detail theoretical 

predictions and potential synthesis routes, including efforts to date, for 5 notional 

EMs: 3,5-dinitro-1,3,5-oxadiazinane (1), bis-adjacent RDX (2), bis-adjacent HMX

(3),4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo 

oxadiazole (4), and the open-cage derivative of CL-20 (5). 

2. Results and Discussion

The properties of the notional 3,5-dinitro-1,3,5-oxadiazinane (1, a), bis-adjacent 

RDX (2, b), bis-adjacent HMX (3, c), 4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-

4H,4'H-5,5'-bisimidazo oxadiazole (4, d), and the open-cage derivative of CL-20

(5, e) molecules (Fig. 1a–e) were predicted using the ARL tools.

7 For the estimation 

of the impact sensitivities, the electrostatic maps on the 0.001 isosurfaces were 

generated with the scalar range of the electrostatic surface potential (ESP) ranging 

from –0.05 to 0.075. Recall that for this visualization methodology, regions of large 

positive charge (i.e., electron deficient regions, labeled as red) over the backbone 

of the structure tend to indicate increased sensitivity. 
2

Fig. 1 Optimized structures a) 1, b) 2, c) 3, d) 4, and e) 5
3

The computed heats of formation and crystalline densities for these molecules are 

presented in Table 1. Additionally, we plot the ESP maps for 1 (Fig. 2a–b), 2

(Fig. 3a–b), 3 (Fig. 4a–b), 4 (Fig. 5a–b), and 5 (Fig. 6a–b) both with and without 

the molecule overlaid on the ESP. Analyzing the images, we would quantify the 

molecules as insensitive for molecule 1, moderately sensitive for molecules 2 and 

4, and sensitive for molecules 3 and 5. Recall however, that this methodology is 

qualitative, and exact values are not determinable. Using the predicted data, we then 

performed Cheetah 7.0 calculations8 to predict the performance parameters. At the 

Chapman-Jouguet (CJ) point, Cheetah yields the values shown in Table 2.

Table 1 Computed heats of formation and crystalline densities for 3,5-dinitro-1,3,5-

oxadiazinane (1), bis-adjacent RDX (2), bis-adjacent HMX (3), 4,4',6,6'-tetranitro-1,1'-bis(Noxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo oxadiazole (4), and the open-cage derivative of CL-20 

(5)

Molecule

Solid Phase Heat of 

Formation

(kcal/mol)

Density

(cm3

)

1 –22.213 1.699

2 81.543 1.886

3 82.797 1.919

4 251.902 2.025

5 113.480 1.919
4

Fig. 2 Electrostatic potential map of 1, a) with and b) without molecule overlay
5

Fig. 3 Electrostatic potential map of 2, a) with and b) without molecule overlay
6

Fig. 4 Electrostatic potential map of 3, a) with and b) without molecule overlay
7

Fig. 5 Electrostatic potential map of 4, a) with and b) without molecule overlay
8

Fig. 6 Electrostatic potential map of 5, a) with and b) without molecule overlay
9

Table 2 Cheetah predicted properties for 3,5-dinitro-1,3,5-oxadiazinane (1), bis-adjacent 

RDX (2), bis-adjacent HMX (3), 4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-

bisimidazo oxadiazole (4), and the open-cage derivative of CL-20 (5)

Molecule Pressure 

(GPa)

Shock 

Velocity 

(km/s)

Temperature 

(K)

Total Energy of 

Detonation (TNT eqv)

(per cc) (per gram)

1 27.514 8.104 3195.8 1.260 1.227

2 37.228 9.175 3671.5 1.644 1.442

3 38.487 9.281 3490.9 1.645 1.418

4 56.124 10.089 5344.1 2.307 1.884

5 38.878 9.362 3809.1 1.732 1.493

Based on these predictions, we began pursuing the synthesis of compounds 1, 2, 

4, and 5. Due to the predicted sensitivity of compound 3, we decided against 

synthesizing this EM. While compound 1 (Fig. 7) is known in the Russian 

literature,

9 the physical properties of this molecule have never been reported. Due 

to the presence of the cyclic ether, it is believed that this material could have 

interesting melt-cast capabilities. While the current synthesis of dinitramine 1

requires the use of energetic compounds throughout the entire synthesis, our 

synthetic approach, if ultimately successful, would represent a safer alternative, 

since the energetic transformations would occur only at the end of the synthesis.

N

O

N O2N NO2

Fig. 7 3,5-dinitro-1,3,5-oxadiazinane (1)

The synthetic approach toward synthesizing dinitramine 1 is summarized in 

Scheme 1. Dibenzylurea (7) was synthesized in high yield by an environmentally 

friendly method without the use of phosgene reagents by reacting dimethyl 

carbonate and benzylamine with a catalytic amount of sodium methoxide. 

Treatment of urea 7 with an excess of paraformaldehyde under acidic conditions 

afforded cyclic ether 8. The next step of the synthesis will be to subject cyclic ether 

8 to hydrogenolysis, followed by nitration. Ring opening of the dinitrourea cyclic 

ether with NaOH, followed by reacidification of the disodium dinitramine salt 

would furnish dinitramine 9 as the open-chain. This material has potential to be a 

high performing EM. Dinitramine 9 can be subjected to polymerization to yield

new energetic polymers. Alternatively, dinitramine 9 can be converted into alkali 

and alkaline earth dinitramine salts, which has pyrotechnic applications in civilian 

fireworks and military pyrotechnic illumination. Finally, treatment of dinitramine 

9 with paraformaldehyde in the presence of heat would result in the desired cyclic 

ether dinitramine 1.
10

Scheme 1. Synthesis of cyclic ether dinitramine 1.

BnN

O

NBn

MeO OMe

O

BnNH2 (2.1 eq),

Na0 (0.20 eq)

MeOH 70 o

C, 12 h

6 (1.0 eq)

BnHN NHBn

O

7 (85%)

Paraformaldehyde (5 eq),

HCl (cat.), pH = 1,

Dioxane:H2O (5:1), 70 o

C,

2 h

O

8 (95%)

1. H2, Pd/C, Ac2O

2. Nitration

3.. NaOH, H2O;

then reacidify

NH

O

HN

9

O2N NO2

Polymerize for energetic binders

Metal salts for pyrotechnics

Paraformaldehyde,

heat

N

O

N

1

O2N NO2

Turning to compound 2, bis-adjacent RDX (Fig. 8), a compound that has never 

been reported in the literature and has appreciably higher predicted performance 

than RDX. RDX has a crystalline density of 1.80 cm3

, a detonation pressure of 34.7 

GPa, and a detonation velocity of 8754 m/s.

10 The comparable performance of this 

molecule to HMX, and its predicted moderate sensitivity make it an interesting 

target for synthesis (NB: HMX has a crystalline density of 1.90 cm3

, a detonation 

velocity of 9150 m/s, and a detonation pressure of 39.3 GPa).

10

N

O2NN

N N

NNO2

N

NO2

NO2 NO2

NO2

2

Fig. 8 Bis-adjacent RDX (2)

It was believed that glycoluril was a logical starting point toward the synthesis of 

bis-adjacent RDX. Glycoluril (10) was synthesized in high yield using the known 

acid-catalyzed condensation procedure between urea and glyoxal. With glycoluril 

in hand, a 1-pot method was developed to form tetracycle 11. Paraformaldehyde 

was employed in a slight excess in slightly alkaline conditions to first afford the 
11

resulting glycoluril tetramethylol. This product was not isolated, but was instead 

treated with t-butylamine with moderate heating. This resulted in the formation of 

a white precipitate, which was filtered, and identified as tetracycle 11. Conversion 

the diurea portion of tetracycle 11 to diaminal 12 was achieved in high yield using 

lithium aluminum hydride, see Scheme 2.

Scheme 2. Synthesis of bis-adjacent RDX.

N

O2NN

N N

NNO2

N

NO2

NO2 NO2

NO2

H2N NH2

O

(2.5 eq)

Glyoxal (2.0 eq),

H2SO4 (cat.),

H2O, 80 o

C, 12 h HN NH

HN NH

O

O

10 (92%)

1. Paraformaldehyde (4.1 eq)

H2O, pH = 10, 70 o

C, 15 h

2. t-BuNH2 (2.2 eq), 40 o

C,

17 h

one-pot reaction

N N

N N

O

O

11 (61%)

N N

LiAlH4 (3.0 eq),

Et2O or Dioxane,

0 o

C to RT, 15 h N N

N N

12 (85%)

N N

Bis-adjacent RDX (2)

If nitrolysis occurs at the

methylene bridgeheads O2NN

N

NO2

N

NO2

NNO2

O2NN NNO2 If nitrolysis occurs a 

ethylene fusion

Dodecagen (13)

Nitration Conditions

With tetracycle 12 in hand, the stage is now set for nitration of this compound via 

the nitrolysis of methylene carbons. This logic is analogous to the Bachmann 

process, in which nitrolysis of methylenes occurs selectively on hexamine to afford 

RDX and HMX. In synthesizing bicyclo-HMX, it has been well established that a 

central hurdle in completing this synthesis was the ability for the fused 

5-membered ring system to undergo ring-opening during nitrolysis depending on 

the nitration conditions used.

11 This phenomenon likely occurs as a way to relieve 

the ring strain of the fused 5-membered ring system. 6-membered rings, however, 

are the most thermodynamically stable, and it is not expected that nitrolysis will 

occur within the 6-membered rings with the 5-membered ring system present.

What is not known at this time is which direction nitrolysis will occur. If nitrolysis 

occurs at the methylene carbons of the bridgehead, then the product that forms 

would be bis-adjacent RDX (2). On the other hand, if nitrolysis occurs 

preferentially at the ethylene position of the ring fusion, then the product would be 
12

the 12-membered macrocycle dodecagen (13). This latter molecule has been

described theoretically by McQuaid as having higher performance than HMX, with 

a crystalline density of 1.93 cm3, a detonation velocity of 9230 m/s, and a 

detonation pressure of 37.0 GPa.

12 Undoubtedly, this latter molecule would be 

interesting, particularly if it could be synthesized in a handful of steps, as detailed 

in Scheme 2.

While compound 3, bis-adjacent HMX (Fig. 9) has also never been reported in the 

literature and has a calculated performance similar to bis-adjacent RDX, as stated 

previously the predicted sensitivity of the former compound appears to be 

appreciably higher. It can therefore be debated as to whether synthesizing bisadjacent HMX is a worthwhile target while other, similar performing yet less 

sensitive notional materials are possible. In light of the calculations performed 

within this report, it was decided that our synthetic efforts would be best focused 

elsewhere.

O2NN N

O2NN N N NNO2

NNO2

N

NO2 NO2

NO2

NO2

3

Fig. 9 Bis-Adjacent HMX (3)

Another compound that is currently in the process of being synthesized is bis-Noxide (4), depicted in Fig. 10. This compound that has exceptionally high 

theoretical performance, yet calculates to have only a moderate sensitivity. Given 

the potential performance of this compound, it is imperative that bis-N-oxide (4) be 

synthesized successfully.

N

N

N

N N

O

N N

O

N

NO2 NO2

NO2 NO2

O

O

-

-

+

+

4

Fig. 10 4,4',6,6'-tetranitro-1,1'-bis(N-oxide)-5,5',6,6'-4H,4'H-5,5'-bisimidazo oxadiazole (4)

A proposed synthesis for bis-N-oxide (4) is summarized in Scheme 3. Imidazole 

(14) can be converted to bisimidazole 15 through a known procedure.14 Subjection 

of this latter compound to benzyl bromide, followed by reduction of the resultant 

diimine with sodium borohydride15 would yield tetrabenzylamine 16. Exposure of 

the alkene moieties of tetrabenzylamine 16 with in situ generated N2O3 would 
13

afford bis-furoxan 17. Conversion of the benzyl groups to the acetates, followed by 

nitrolysis would afford the sought after bis-N-oxide 4.

Scheme 3. Synthesis of bis-N-oxide 4.

N

N

N

N N

O

N N

O

N

NO2 NO2

NO2 NO2

O

O

-

-

+

+

4

N N H

14

1. BnBr (4.0 eq),

KOt

Bu (2.0 eq), THF

2. NaBH4 (2.5 eq),

CH3CN

NH4OAc (2.5 eq),

Glyoxal (1.0 eq), H2O,

40-50 o

C

N

H

N

N

H

N

15

N

N

N

N

16

Bn

Bn

Bn

Bn

NaNO2 (2.5 eq),

AcOH, H2O,

0 o

C-RT

N

N

N

N N

O

N N

O

N

Bn Bn

Bn Bn

O

O

-

-

+

+

17

1. TMSOTf (4.0 eq),

Ac2O

2. Nitration

Finally, the most elusive target thusfar has been a plausible synthesis for the openchain version of CL-20 (Fig. 11). This molecule has better calculated performance 

than bis-adjacent HMX, and bis-adjacent RDX. Although it is calculated to be quite 

sensitive, as CL-20 is able to be synthesized and handled, it is believed that the 

open-chain version of the molecule, which is less strained, will also be able to be 

handled safely, assuming it can be synthesized.

N

NO2

NO2

N

N

NO2

NO2

N

NO2

N

N

NO2

5

Fig. 11 Open-chain CL-20 (5)

A proposed synthetic pathway toward the synthesis of open-chain CL-20 is 

summarized in Scheme 4. Disilyl-1,4-dihydropyrazine (18) can be prepared from 

the known dissolving metal reduction route from commercially available 

pyrazine.

13 Osmium-catalyzed dihydroxylation of the diene via the Upjohn 

procedure would furnish tetraol 19 in the required syn-configuration, which could 

be converted to tetra-mesylate 20. Reaction of this mesylate with methylene bisacetamide, followed by global nitration would yield 5; the open-chain version of 

CL-20.
14

Scheme 4. Synthesis of open-chain CL-20.

N

TBS

TBS

N

N

Ac

Ac

N

Ac

N

N

Ac

21

N

TBS

TBS

N

18

OsO4, NMO, t-BuOH

N

TBS

TBS

N

19

HO

HO

OH

OH

MsCl, Ett

N,

CH2Cl2 N

TBS

TBS

N

20

MsO

MsO

OMs

OMs

AcN NAc

H H

NaH, THF

Nitration

N

NO2

NO2

N

N

NO2

NO2

N

NO2

N

N

NO2

5

3. Conclusions

The ARL-developed software tools were used to predict the heats of formation and 

crystalline densities of notional compounds 1–5. Using this predicted data, we then 

ran Cheetah calculations to predict the performance of these novel materials. 

Additionally, we predicted the qualitative impact sensitivity of these compounds

using electrostatic potential maps. Based on the theoretical models, synthetic efforts 

were initiated for compounds 1 and 2, and synthetic pathways to make compounds 

4 and 5 were provided. Due to the high predicted sensitivity, coupled with 

inadequate performance compared to bis-adjacent RDX, bis-adjacent HMX (3) was 

not considered further for synthesizing. Bis-N-oxide 4 was determined to be a very

powerful potential explosive, with a density of 2.025 cm3, a detonation pressure of 

56.124 GPa, and a detonation velocity of 10.089 km/s. Efforts to synthesize this 

molecule, as well as molecules 1, 2, and 5 continue.
15

4. References

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113, 5813. 

2. Byrd EFC, Rice BM. J. Phys. Chem. A 2009;113(1): 345–352.

3. Rice BM, Hare JJ, Byrd EFC. J. Phys. Chem. A. 2007;111(42):10874–10879.

4. Rice BM, Byrd EFC. J. Comp Chem. 2013;34(25): 2146-2151.

5. Rice BM, Hare JJ. J. Phys. Chem. A 2002;106(9):1770–1783.

6. Byrd EFC. Theoretical Prediction of the Heat of Formation, Density and 

Relative Sensitivity for 3,7-dinitro-[1,2,4]triazolo[5,1-c][1,2,4]triazin-4-

amine. Aberdeen Proving Ground (MD): Army Research Laboratory (US): 

2015 Apr. Report No: ARL-TN-XXXX.

7. Byrd EFC. On the Failure of Correlating Partitioned Electrostatic Surface 

Potentials Using Bader’s Atoms-in-Molecules Theory to Impact Sensitivities. 

Aberdeen Proving Ground (MD): Army Research Laboratory (US): 2013 Sept. 

Report No: ARL-TR-6206.

8. Bastea S, Fried LE, Glaeseman KR, Howard WM, Kuo IFW, Souers PC,

Vitello PA. Cheetah 7.0 thermochemical code (Energetic Materials Center, 

Lawrence Livermore National Laboratory) 2012.

9. Ishchenko MA, Nikolaev VD, Sokolov AA. Russian Journal of Organic 

Chemistry. 1997;33:1794–1797.

10. Politzer, P, Murray JS, Cent. Eur. J. Energ. Mater. 2011;8:209–220.

11. Agrawal JP, Hodgson RD. Organic Chemistry of Explosives, 2007, John 

Wiley & Sons Ltd., West Sussex, England, 272.

12. McQuaid MJ, Drake GW. The design and characterization of alipolycyclic 

amines with the potential to be precursors for the affordable production of 

notional nitramines. Aberdeen Proving Ground (MD): Army Research 

Laboratory (US): 2009 Jan. Report No.: ARL-TR-4695.

13. Baumgarten J, Bessenbacher C, Kaim W, Stahl J. J. Am. Chem. Soc. 1989;

111:2126–2131.
16

14. Paraskos AJ, Cooke ED, Caflin KC. Propellants, Explos. Pyrotech., 2014;40:

46–49.

15. (a) Hashimoto T, Hoshino R, Hatanaka T, Ohki Y, Tatsumi K. 

Organometallics. 2014;33:921–929; (b) Plath MW, Scharf HD, Raabe, G,

Krueger C. Synthesis. 1990;10:951–955.
17

List of Symbols, Abbreviations, and Acronyms

Ac Acetyl

APG Aberdeen Proving Ground

ARL US Army Research Laboratory

Bn Benzyl

CH2Cl2 Methylene Chloride

DFT Density functional theory

CJ Chapman-Jouguet

DSRC Department of Defense (DOD) Supercomputing Resource Center

EM Energetic Material

ESP electrostatic surface potential

Et Ethyl

cm3 grams per cubic centimeter

HCl hydrochloric acid

HEDM High Energy Dense Material

kcal/mol kilocalories per mole (unit of energy)

KS-DFT Kohn-Sham density functional theory

NaOH sodium hydroxide

NMO N-morpholine-N-oxide

Ms Methanesulfonyl

t-Bu tert-butyl

THF Tetrahydrofuran

TBS tert-butyldimethyl silyl

Tf Triflate

TMS Trimethylsilyl
18

1 DEFENSE TECHNICAL

(PDF) INFORMATION CTR

DTIC OCA

2 DIRECTOR

(PDF) US ARMY RESEARCH LAB

RDRL CIO LL

IMAL HRA MAIL & RECORDS

MGMT

1 GOVT PRINTG OFC

(PDF) A MALHOTRA

1 US ARMY ARDEC

(PDF) A DISTASIO

1 US ARMY ARDEC

(PDF) S NICOLICH

1 NAVAL SURF WARFARE

(PDF) CNTR

H HAYDEN 

18 DIR USARL

(PDF) RDRL WM

B FORCH

RDRL WMM

J ZABINSKI

RDRL WML

M ZOLTOSKI

RDRL WML A

W OBERLE

RDRL WML B

N TRIVEDI

J MORRIS

B RICE

E BYRD

RDRL WML C

S AUBERT

J SABATINI

W SHERRILL

J BANNING

RDRL WML D

R BEYER

RDRL WML E

P WEINACHT

RDRL WMP

D LYON

RDRL WML G

W DRYSDALE

RDRL WML H

J NEWILL

RDRL WMP G

R EHLERS