Propellants, Explosives, Pyrotechnics 31, No.

6 (2006) 477

Full Paper

Synthesis and Characterization of Two Potential Energetic Azido

Esters
Chandra Shekhar Pant*, Rashmi Moreshwar Wagh, Jaya Kamalesh Nair*, Girish Mukund Gore,
Sethuramasharma Venugopalan
High Energy Materials Research Laboratory, Pune 411 021 (India)
DOI: 10.1002/prep.200600065

Abstract above considerations, two new energetic azido esters have

been synthesized and characterized during this work.
Two new energetic azido esters named 1,3-bis(azidoacetoxy)-2- These azido esters are synthesized from easily available
azidoacetoxymethyl-2-ethylpropane (I) and 1,3-bis(azidoace- raw materials in simple steps.
toxy)-2,2-bis(azidomethyl)propane (II), have been synthesized
and characterized by IR, NMR and Elemental Analysis. Thermal
studies revealed that azido esters I and II are stable up to 180 8C
and their glass transition temperatures are
47 8C and
52 8C,
respectively.

Keywords: Binders, Plasticizers, Azido Polymers, Glass Transition

Temperature

1 Introduction

Azido polymeric binders, viz glycidyl azide polymer

(GAP), copolymers of 3,3-bis(azidomethyl)oxetane
(BAMO) and 3-azidomethyl-3-methyloxetane (AMMO)
etc., have certain drawbacks associated with them such as
poor mechanical properties and low solid loadings in
energetic formulations [1]. In order to overcome these
problems, the use of various plasticizers along with the
binder has been suggested. Azido ester plasticizers have
received good attention in this regard, and have been
reported to have better stability and good compatibility with
binders like GAP and poly-3-nitratomethyl-3-methyloxe-
tane (poly-NIMMO) [2] as compared with known nitrate
ester plasticizers, e.g. trimethylolethane trinitrate
(TMETN) and 1,2,4-butanetriol trinitrate (BTTN).
The most attractive feature of azido compounds is their
high heat of formation. The exothermic decomposition of
these organic azido compounds exclusively gives nitro-
genrich smokeless burning products. The azido group
contributes to the positive heat of formation of about
356 kJ/mol. However, an increase in number of azido groups
results in increase in viscosity of the azido esters. PETKAA
is reported to have a high viscosity (1612 mPa · s at 25 8C) [1],
whereas its analog azido ester based on trimethylolpropane
(TMP) has a viscosity of 82 mPa · s at 25 8C. In view of the
* Corresponding authors; e-mail: cspant79@yahoo.com (Chandra
Shekhar Pant) or jaya_nair42@yahoo.com (J. K. Nair).
Scheme 1. Schemes of the compounds I and II.
2 Experimental
2.1 General
All the reactions were monitored by precoated silica gel
60 F254 (Merck) TLC plates. The spots on TLC plates were
visualized by iodine vapor or under UV light. 1H NMR
spectra were recorded on a Bruker-300 MHz instrument
using tetra methyl silane (TMS) as an internal reference and
CDCl3 as solvent. IR spectra were recorded on a Perkin
Elmer FT-IR 1605 spectrophotometer as a neat sample.
Elemental analyses were carried out on a Perkin Elmer
Elemental Analyzer EA-1110. All the chemicals were
obtained from commercial suppliers and were used without
further purification except BAMO, which was synthesized
in the laboratory [3].
Differential Scanning Calorimetry (DSC) studies were
carried out on a Perkin Elmer DSC-7 instrument operating
at a heating rate of 10 8C/min in nitrogen atmosphere with 1
to 2 mg of sample. Thermal decomposition studies were also
undertaken on a Mettler Toledo TG/SDTA-8551. The heats
0
of formation for the azido esters in gaseous state (DfH ðgÞ )
were theoretically predicted by group additivity method [4].
0
The azido groupAs contribution to the overall DfH ðgÞ was

H 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

478
extracted from the reported thermochemical measurements
[5]. The sensitivity to impact was determined by the Fall
Hammer Method using 2 kg drop weight. The results are
reported in terms of height for 50% probability of explosion
(h50%) of the sample. The friction sensitivity of the com-
pounds was measured on a Julius PeterAs apparatus till there
was no explosion / ignition in five consecutive test samples at
that weight. The results obtained for impact and friction
sensitivity were within the uncertainty limits of  5 cm and
 0.2 kg, respectively [6].
2.2 Synthesis
The synthesis of I and II involves two similar steps, which
are
(i) Reaction of alcohol with chloroacetic acid to make
chloroacetate.
(ii) Azidation of chloroacetate to azidoacetate.
These reactions are represented in the schemes below.
1,3-Bis(chloroacetoxy)-2-chloroacetoxymethyl-2-ethyl
propane: To tris(hydroxymethyl) propane (TMP) (5 g,
37.26 mmol) dissolved in dry toluene (80 mL), chloroacetic
acid (15.86 g, 167.85 mmol) and p-toluene sulphonic acid
(0.14 g, 0.75 mmol) were added. The reaction mixture was
refluxed with efficient removal of water using a Dean and
Stark assembly till the completion of reaction (5 – 7 h).
Excess toluene was then distilled out and the residue
obtained was dissolved in dichloromethane. The resulting
solution was washed with saturated aqueous NaHCO3 and
brine. The organic layer was dried over Na2SO4. Evapora-
tion of solvent yielded chloroacetate (12.45 g, 34.28 mmol),
purified by column using silica. Colorless liquid (92%).
Elemental analysis calculated for C12H17Cl3O6 (363.62) C:
39.64%, H: 4.71%. Found C: 39.53%, H: 4.45%. IR (Neat,
cm
1) 2966 (C
H str), 1757 (C¼O str), 788 (C
Cl str). 1H
NMR (300 MHz, CDCl3, Me4Si) d 0.93 (3H, t, J ¼ 7.5 Hz,
CH3), 1.54 (2H, q, J ¼ 7.5 Hz, CH2CH3), 4.09 (6H, s, 3 
CH2Cl), 4.16 (6H, s, 3  CH2O.OC).
Scheme 2. Synthesis of I.
Scheme 3. Synthesis of II.
Prop., Explos., Pyrotech. 31, No. 6, 477 – 481 www.pep.wiley-vch.de
C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, S. Venugopalan
1,3-Bis(azidoacetoxy)-2-azidoacetoxymethyl-2-ethyl
propane (I): To the above, chloroacetate (3.63 g, 10 mmol)
dissolved in 30 mL DMSO (2%water), NaN3 (2.93 g,
45 mmol) was added with cooling. The reaction mixture
was slowly warmed to 40 8C and stirred till the completion of
reaction (25 – 30 h). The reaction mixture was then poured
into iced water and extracted with dichloromethane. The
dichloromethane extract was washed 2 – 3 times with brine
and then dried over Na2SO4. Evaporation of solvent yielded
azidoacetate. Careful filtration through silica gel bed gave
pure azidoacetate (3.37 g, 8.8 mmol). Pale yellow liquid
(88%). Elemental analysis calculated for C12H17N9O6
(383.32) C: 37.60%, H: 4.47%, N: 32.89%. Found C:
36.89%, H: 4.33%, N: 32.36%. IR (Neat, cm
1) 2969 (C
H
str), 2106 (N3 str), 1746 (C¼O str). 1H NMR (300 MHz,
CDCl3,) d 0.94 (3H, t, J ¼ 7.5 Hz, CH3), 1.55 (2H, q, J ¼
7.5 Hz, CH2CH3), 3.91 (6H, s, 3  CH2N3), 4.18 (6H s, 3 
CH2O.OC).
2,2-Bis (azidomethyl) propane-1,3-diol: To the BAMO
(5 g, 29.73 mmol), 30 mL of 0.5 N H2SO4 was added. The
stirred mixture was refluxed for 3 to 4 h. On completion of
reaction, the reaction mixture was cooled and neutralized
with solid NaHCO3. The resulting mixture was extracted
with ethyl acetate (30 mL  2). The extract was washed with
brine and then dried over Na2SO4, followed by evaporation
of solvent in vacuum to yield diol (5.04 g, 27.06 mmol).
Colorless liquid (91%). Elemental analysis calculated for C5
H10N6O2 (186.17) C: 32.26%, H: 5.41%, N: 45.14%. Found C:
31.74%, H: 5.55%, N: 45.58%. IR (Neat, cm
1) 3390 (br,
O
H str), 2940 (C
H str), 2107 (N3 str). 1H NMR (300 MHz,
CDCl3,) d 3.26 (2H, br s, 2  OH, exchangeable with
deuterium), 3.38 (4H, s, 2  CH2N3), 3.57 (4H, s, 2 
CH2OH).
2,2-Bis(azidomethyl)-1,3-bis(chloroacetoxy) propane: To
the diol (5 g, 26.85 mmol) dissolved in dry toluene (80 mL),
chloroacetic acid (7.61 g, 80.57 mmol) and p-toluene sul-
phonic acid (0.1 g, 0.5 mmol) were added. The reaction
mixture was refluxed with efficient removal of water using a
Dean and Stark assembly till the completion of reaction (5 –
7 h). Excess toluene was then distilled out and the residue
H 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis and Characterization of Two Potential Energetic Azido Esters 479

obtained was dissolved in dichloromethane. The resulting

solution was washed with saturated aqueous NaHCO3 and
brine. The organic layer was dried over Na2SO4. Evapora-
tion of solvent yielded chloroacetate (8.29 g, 24.43 mmol).
Colorless liquid (91%). Elemental analysis calculated for
C9H12Cl2N6O4 (339.15) C: 31.87%, H: 3.57%, N: 24.78%.
Found C: 31.95%, H: 3.15%, N: 25.26%. IR (Neat, cm
1)
2958 (C
H str), 2108 (N3 str), 1756 (C¼O str), 790 (C
Cl str).
1
H NMR (300 MHz, CDCl3) d 3.46 (4H, s, 2  CH2N3), 4.10
(4H, s, 2  CH2Cl), 4.14 (4H, s, 2  CH2O.OC).
1,3-Bis(azidoacetoxy)-2,2-bis(azidomethyl) propane (II):
To the corresponding chloroacetate (3.4 g, 10 mmol) dis-
solved in 30 mL DMSO (2% water), NaN3 (1.95 g, 30 mmol)
was added with cooling. The reaction mixture was
1
slowly warmed to 40 8C and stirred till the completion
Figure 1. H NMR of I. of reaction (25 – 30 h). The reaction mixture was then
poured into iced water and extracted with dichloromethane.
The dichloromethane extract was washed 2 – 3 times with
brine and then dried over Na2SO4. Evaporation of solvent
yielded azidoacetate. Careful filtration through silica gel
bed gave pure azidoacetate (3.38 g, 9.6 mmol). Pale yellow
liquid (96%). Elemental analysis calculated for C9H12N12O4
(352.28) C: 30.69%, H: 3.43%, N: 47.71%. Found C:
31.07%, H: 3.01%, N: 48.22%. IR (Neat, cm
1) 2932 (C
H
str), 2109 (N3 str), 1752 (C¼O str). 1H NMR (300 MHz,
CDCl3) d 3.47 (4H, s, 2  CH2N3), 3.93 (4H, s, 2  OCO.
CH2N3), 4.16 (4H, s, 2  CH2O.OC).

2.3 Evaluation

To study the plasticizing effect of these azidoesters on the

binder GAP, laboratory scale mixing of these esters with
1
Figure 2. H NMR of II. GAP was carried out at room temperature in the ratio 1 : 1.

Figure 3. DSC Thermogram of I.

H 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Prop., Explos., Pyrotech. 31, No. 6, 477 – 481
480 C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, S. Venugopalan

Figure 4. DSC Thermogram of II.

3 Results and Discussion
The compounds I and II as well as the intermediates
involved in their synthesis have been fully characterized by
Elemental Analysis, IR, and 1H NMR. The absence of C
Cl
stretching frequency ( 789 cm
1) and the presence of N3
stretching frequency ( 2108 cm
1) in the IR spectra of I and
II clearly confirm the substitution of
Cl by
N3 group. 1H
NMR (Fig. 1 and 2) and Elemental Analysis data also
confirm the synthesis of I and II. The purity of the samples is
evidenced by the fact that no significant additional peaks
were observed in 1H NMR spectra. Starting materials
required for the synthesis of the above azidoesters are
cheap and yields are high.
Thermal studies by DSC and TGA (Table 1) showed the
thermal stability up to 180 8C. DSC (Fig. 3 and 4) revealed
exothermic decomposition with Tmax at 254 8C and 246 8C,
and the heat release of the order of 2130 J/g and 3098 J/g for
I and II respectively. The glass transition temperatures (Tg)
of the compounds I and II were found to be
47 8C and

52 8C respectively, which are sufficiently low, suitable for
their application as plasticizer in explosive and propellant
formulations. The weight loss pattern of the compounds I
and II in their TGA thermogram were quite different.
Compound I showed two-step decomposition with 47% and
29% weight loss in the temperature range of 180 8C to
279 8C, and 281 8C to 387 8C, respectively. On the other hand
compound II showed single-step decomposition with 83%
weight loss in the temperature range of 181 8C to 278 8C.
Table 1 shows the values for impact and friction sensitiv-
ity. Test results show that both the compounds were fairly
insensitive to mechanical stimuli.
Preliminary evaluation studies of these azido esters show
their good compatibility with binder GAP, and also in
the case of II, lowering of Tg was observed, as shown in
Table 2.

Table 1. Thermal, physical and sensitivity properties of the azido esters.

Properties Compound (I ) Compound (II )
DSC, Tmax (8C ) 254.5 245.8
Heat release, DH ( J/g) 2129.6 3096.7
Glass Transition Temperature, Tg (8C)
47.0
51.9
TGA, Weight Loss 47.3% (180 8C – 279 8C)
29.4% (281 8C – 387 8C) 83.3% (181 8C – 278 8C)
Oxygen Balance (%)
110.6
90.8
0
Heat of Formation (DfH ðgÞ ) (kJ/mol)
157.5 605.6
Viscosity, at 25 8C (mPa · s) 82 205
Impact Sensitivity (cm) > 170 > 170
Friction Sensitivity (kg) 36 36

Prop., Explos., Pyrotech. 31, No. 6, 477 – 481 www.pep.wiley-vch.de H 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis and Characterization of Two Potential Energetic Azido Esters 481

Table 2. Effect of azido esters on Tg of GAP. [2] D. Drees, D. Lçffel, A. Messmer, K. Schmid, Synthesis and
Characterization of Azido Plasticizer, Propellants, Explos.,
Composition Tg (8C ) Pyrotech. 1999, 24, 159.
GAP
51 [3] J. K. Nair, R. S. Satpute, G. B. Polke, T. Mukundan, S. N.
GAP þ I (1 : 1)
52 Asthana, H. Singh, Synthesis and Characterization of Bis(azi-
GAP þ II (1 : 1)
55 domethyl)oxetane and its Polymer and Copolymer with Tetra-
hydrofuran, Defence Science Journal 2002, 52, 147.
[4] a) S. W. Benson, J. H. Buss, Additivity Rules for the Estimation
of Molecular Properties. Thermodynamic Properties, J. Chem.
Phys. 1958, 29, 546. b) P. W. Cooper, Explosives Engineering,
4 Conclusions VCH Publishers Inc., New York, 1996, 135.
[5] A. Lee, C. K. Law, A. Makino, Aerothermochemical Studies of
The synthesis of two potential energetic azido esters I and Energetic Liquid Materials. 3. Approximate Determination of
Some Thermophysical and Thermochemical Properties of
II have been established at multigram level. Structural Organic Azides, Combust. Flame 1989, 78, 263.
features were confirmed by IR, 1H NMR, and Elemental [6] L. Avrami, R. Hutchinson, The Sensitivity to Impact and
Analysis. Low Tg, good thermal stability, high heat release Friction, in: H. D. Fair, R. F. Walker (Eds.), Energetic Materials.
capabilities and insensitivity towards impact and friction are Vol. 2. Technology of Inorganic Azides, Plenum Press, New
characteristics of these azido esters of great interest for their York, 1977, p. 111.
application in propellant / explosive formulations.

Acknowledgement

The authors wish to thank Shri Subhananda Rao, Director of

5 References HEMRL, for his guidance and for permission to publish this work.
[1] D. Drees, D. Lçffel, A. Messmer, K. Schmidt, Synthesis and
Characterization of Azido Plasticizer, 31st Int. Annual Confer-
ence of ICT, Karlsruhe, Germany, June 27 – 30, 2000, p. 52 – 1. (Received December 20, 2005; Ms 2005/141)

H 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Prop., Explos., Pyrotech. 31, No. 6, 477 – 481