Propellants, Explosives, Pyrotechnics 32, No.
6 (2007)
Full Papers
Synthesis and Characterization of First Generation Dendritic
Azidoesters
Chandra Shekhar Pant*, Rashmi M. Wagh, Jaya K. Nair**, Girish M. Gore, Mukundan Thekkekara,
Sethuramasharma Venugopalan
High Energy Materials Research Laboratory, Pune 411 021 (India)
Received: January 23, 2007, revised version: May 17, 2007; Ms 2007/102
DOI: 10.1002/prep.200700050
Abstract
A new class of first generation azido-terminated dendritic
esters have been synthesized by four step processes. The final
products and the intermediates are characterized by IR, 1H NMR,
and elemental analysis. Thermal studies revealed that these
dendritic esters were thermally stable up to
190 8C and the
glass transition temperature was found to be  54 and  32 8C,
respectively.
Keywords: Azidopolymers, Binders, Dendrimers, Energetic
Materials, First Generation Dendrimers, Plasticizers
1 Introduction
Recent research in the field of energetic material
formulations (explosives/propellants) is aimed at develop-
ing high energy binders, better in performance than the
conventional nonenergetic binders, viz. hydroxy-terminated
polybutadiene (HTPB), carboxy-terminated polybutadiene
(CTPB), hydroxy-terminated polyethylene (HTPE), etc. as
well as compatible with ecofriendly oxidizers like hydrazi-
nium nitroformate (HNF), ammonium dinitramide (ADN),
etc. Among the azido polymeric binders, glycidyl azido
polymer (GAP) and polymers of azido oxetanes like BAMO
and AMMO are well reported [1]. Though these binders are
energetic, they exhibit certain drawbacks like poor proces-
sibility, low solid loading, and inferior mechanical proper-
ties. In order to overcome these problems, there is a need to
develop suitable additives which can act as processing aid,
improve solid loading, and also impart additional energy to
the formulations.
In recent years, azidoester plasticizers in combination
with azido-polymeric binders have received good attention.
Compared to known nitrate ester plasticizers, for example
* Corresponding author; e-mail: cspant79@yahoo.com
** Additional corresponding author; e-mail: jaya_nair42@yahoo.
com
D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
461
TMETN and BTTN, azidoester plasticizers have been
reported to have better stability and good compatibility
with azido binders like GAP [2].
Dendrimers are repetitively branched three-dimensional
(3D) molecules with all branches emanating from a central
core. Compact 3D structure of dendrimer molecules allows
them to easily flow past each other under applied stress.
They show low Tg and low viscosity due to lack of restrictive
interchain entanglement in contrast to most linear polymers.
The dendrimer additives are able to behave as lubricants
during processing and toughening agent in the final blend
formulation [3, 4].
Considering the above facts, efforts have been made to
incorporate the azido group into a dendritic structure. Two
first generation [G-1] terminally azido-functionalized den-
dritic esters have been synthesized (Schemes 1 and 2) during
this study.
2 Experimental Part
2.1 General
All chemicals were obtained from commercial suppliers
and were used without further purification except the
catalyst dimethyl aminopyridinium-p-toluenesulfonate
(DPTS), which was prepared as per the process developed
by Moore and Stupp [5]. One of the starting materials,
isopropylidene-2,2-bis(hydroxymethyl)propionic acid was
prepared from 2,2-bis(hydroxymethyl)propionic acid
(DMPA) and 2,2-dimethoxypropane by the reported meth-
od [6]. N,N-Dicyclohexylcarbodiimide (DCC) was used as
obtained.
All 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 tetramethylsilane (TMS) as an internal reference and
462 C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, M. Thekkekara, S. Venugopalan

Scheme 1. Synthesis of [G-1]-(N3)6.

Scheme 2. Synthesis of [G-1]-(N3)8.

CDCl3 or DMSO-d6 as a solvent. IR spectra were recorded
on a Perkin-Elmer FT-IR 1605 spectrophotometer either as
neat sample or in KBr pellet. Elemental analyses were
carried out on a Perkin-Elmer Elemental Analyzer EA-
1110.
Differential scanning calorimetry (DSC) studies were
carried out on a Perkin-Elmer DSC-7 instrument operating
at a heating rate of 10 8C min1 in nitrogen atmosphere with
1 – 2 mg of sample. Thermal decomposition studies were
also undertaken on a Mettler Toledo TG/SDTA-8551. The
heats of formation for the azidoesters in gaseous state
0
(Df HðgÞ ) were theoretically predicted by group additivity
method [7]. The azido groupKs contribution to the overall
0
Df HðgÞ was extracted from the reported thermochemical
measurements [8]. The sensitivity to impact was determined
by the Drop 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
compounds was measured on a Julius PeterKs apparatus till
there was no explosion/ignition in five consecutive test

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Synthesis and Characterization of First Generation Dendritic Azidoesters
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 [9].
2.2. Synthesis
The steps involved in the synthesis of azido-terminated
dendrimers [G-1]-(N3)6 and [G-1]-(N3)8 are represented in
the schemes above.
2.2.1 Preparation of the First Generation Acetonide-Pro-
tected Dendrimer
Isopropylidene-2,2-bis(hydroxymethyl)propionic acid
(3.26 g, 18.7 mmol), Tris(hydroxymethyl)propane (TMP)
(0.8 g, 6 mmol) or pentaerythritol (0.61 g, 4.5 mmol), and
DPTS (1.05 g, 3.6 mmol) were mixed in 30 mL of dichloro-
methane (dry). DCC (4.6 g, 22.3 mmol) was added and the
mixture was stirred at 25 8C for 15 h. The side product,
substituted urea and unused catalyst were filtered off.
Evaporation of dichloromethane gave crude product, which
was purified by column chromatography over silica gel
eluting with ethyl acetate/hexane (25 : 75 v/v) to afford
acetonide-protected dendrimer.
[G-1]-(O2C (CH3)2)3: Colorless oil, 3.32 g (91.8%).
Elemental analysis: (C30H50O12)n (602.71)n: Calcd. C
59.78%, H 8.36%; Found C 59.43%, H 8.64%.
IR (Neat, cm1): 2977 (CH str), 1735 (C¼O str).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 0.93 (3H, t, J ¼
7.5 Hz, CH2CH3), 1.14 (9H, s, CH3), 1.35 (9H, s, CH3),
1.42 (9H, s, CH3), 1.55 (2H, q, J ¼ 7.5 Hz, CH2CH3), 3.63
(6H, d, Jgem ¼ 11.7 Hz, CHH’O), 4.13 (6H, s, CH2O.OC),
4.17 (6H, d, Jgem ¼ 11.7 Hz, CHH’O).
[G-1]-(O2C (CH3)2)4: White solid, 3.25 g (95.3%).
Elemental analysis: (C37H60O16)n (760.88)n: Calcd. C
58.41%, H 7.95%; Found C 58.74%, H 8.26%.
IR (Neat, cm1): 2986 (CH str), 1738 (C¼O str).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 1.14 (12H, s,
CH3), 1.35 (12H, s, CH3), 1.42 (12H, s CH3), 3.64 (8H, d,
Jgem ¼ 12 Hz, CHH’O), 4.17 (8H, d, Jgem ¼ 12 Hz,
CHH’O), 4.26 (8H, s, CH2O.OC).
2.2.2 Preparation of the First Generation Hydroxy-Termi-
nated Dendrimer
Acetonide-protected dendrimer (5.3 mmol) was dis-
solved in 30 mL of methanol. Two grams of Amberlite 120
Hþ resinN was added to the solution and the reaction mixture
was stirred for 3 h at 25 8C. Upon completion of the reaction,
the resin was removed by filtration. The methanol was
evaporated to give hydroxy-terminated dendrimer.
[G-1]-(OH)6: White solid, 2.49 g (97.2%).
Elemental analysis: (C21H38O12)n (482.51)n: Calcd. C
52.27%, H 7.94%; Found C 51.77%, H 8.05%.
D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467
463
IR (KBr, cm1): 3325 (OH str), 2941 (CH str), 1730
(C¼O str).
1
H NMR (300 MHz, DMSO-d6): d (ppm) ¼ 0.76 (3H, t,
J ¼ 7.2 Hz, CH2CH3), 0.96 (9H, s, CH3), 1.37 (2H, q, J ¼
7.2 Hz, CH2CH3), 3.30 (broad signal, OH and CH2O),
3.88 (6H, s, CH2O.OC).
[G-1]-(OH)8: White solid, 3.05 g (95.9%).
Elemental analysis: (C25H44O16)n (600.62)n: Calcd. C
49.99%, H: 7.38%; Found C 51.50%, H 7.44%.
IR (KBr, cm1): 3325 (OH str), 2941 (CH str), 1730
(C¼O str).
1
H NMR (300 MHz, DMSO-d6/deuterium exchange): d
(ppm) ¼ 1.03 (12H, s, CH3), 3.39 (8H, d, Jgem ¼ 10.2 Hz,
CHH’OH), 3.47 (8H, d, Jgem ¼ 10.2 Hz, CHH’OH), 4.06
(8H, s, CH2O.OC).
2.2.3 Preparation of the First Generation Tosyl-Terminated
Dendrimer
Hydroxy-terminated dendrimer (4.14 mmol) was dis-
solved in 20 mL of pyridine. p-Toluene sulfonylchloride
(1.5 equivalent for each hydroxyl group) was added to the
solution at 0 8C. The reaction mixture was stirred at 25 8C for
48 h and then poured into crushed ice, neutralized with 5 N
HCl, followed by extraction with CH2Cl2. The CH2Cl2
extract was washed with saturated aq. NaHCO3 and then
2 – 3 times with brine followed by drying over Na2SO4.
Evaporation of solvent yielded tosyl-terminated dendrimer.
[G-1]-(OTs)6: Colorless thick liquid, 5.04 g (86.4%).
Elemental analysis: (C63H74O24S6)n (1407.65)n: Calcd. C
53.75%, H 5.30%; Found C 55.00%, H 5.44%.
IR (Neat, cm1): 3035 (Ar CH str), 2957 (CH str), 1741
(C¼O str).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 0.80 (3H, t, J ¼
7.5 Hz, CH2CH3), 1.13 (9H, s, CH3), 1.35 (2H, q, J ¼
7.5 Hz, CH2CH3), 2.45 (18H, s, ArCH3), 3.96 (6H, s,
CH2O.OC), 3.97 (6H, d, Jgem ¼ 9.2 Hz, CHH’O), 4.13
(6H, d, Jgem ¼ 9.2 Hz, CHH’O), 7.34 (12H, d, J ¼ 8.4 Hz,
ArH), 7.71 (12H, d, J ¼ 8.4 Hz, ArH).
[G-1]-(OTs)8: Colorless thick liquid, 6.84 g (90.1%).
Elemental analysis: (C81H92O32S8)n (1834.13)n: Calcd. C
53.04%, H 5.06%; Found C 53.87%, H 5.32%.
IR (Neat, cm1): 3053 (Ar CH str), 2984 (CH str), 1744
(C¼O str).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 1.12 (12H, s,
CH3), 2.42 (24H, s, ArCH3), 3.96 (8H, d, Jgem ¼ 9.9 Hz,
CHH’O), 4.07 (8H, s, CH2O.OC), 4.14 (8H, d, Jgem ¼
9.9 Hz, CHH’O), 7.31 (16H, d, J ¼ 8.1 Hz, ArH), 7.69
(16H, d, J ¼ 8.1 Hz, ArH).
2.2.4 Preparation of First Generation Azido-Terminated
Dendrimer
Tosyl-terminated dendrimer (3.19 mmol) was dissolved in
30 mL of dimethylsulfoxide. NaN3 (1.5 equivalent for each
tosyl group) was added to the solution at 0 8C. The reaction
464 C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, M. Thekkekara, S. Venugopalan
mixture was warmed to 75 8C and stirred till the completion
of reaction (
30 h). The reaction mixture was poured into
iced water and extracted with CH2Cl2. The CH2Cl2 extract
was washed 2 – 3 times with brine and dried over Na2SO4.
Evaporation of solvent yielded crude product, which was
purified by passage through a small silica gel packed column
eluting with CH2Cl2 to yield azido-terminated dendrimer.
[G-1]-(N3)6: Colorless liquid, 1.8 g (89.2%).
Elemental analysis: (C21H32O6N18)n (632.59)n: Calcd. C
39.87%, H 5.10%, N 39.86%; Found C 39.98%, H 4.50%, N
39.30%.
IR (Neat, cm1): 2973 (CH str), 2109 (N3 str), 1737 (C¼O
str).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 0.96 (3H, t, J ¼
7.5 Hz, CH2CH3), 1.24 (9H, s, CH3), 1.52 (2H, q, J ¼
7.5 Hz, CH2CH3), 3.52 (6H, d, Jgem ¼ 8.1 Hz, CHH’N3),
3.58 (6H, d, Jgem ¼ 8.1 Hz, CHH’N3), 4.1 (6H, s, CH2
O.OC).
[G-1]-(N3)8: White solid, 2.34 g (91.6%).
Elemental analysis: (C25H36O8N24)n (800.73)n: Calcd. C
37.50%, H 4.53%, N 41.98%; Found C 38.13%, H 4.72%, N
41.48%.
IR (Neat, cm1): 2980 (CH str), 2110 (N3 str), 1734 (C¼O
str).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 1.25 (12H, s,
CH3), 3.52 (8H, d, Jgem ¼ 12 Hz, CHH’N3), 3.58 (8H, d,
Jgem ¼ 12 Hz, CHH’N3), 4.2 (8H, s, CH2O.OC).
1
Figure 1. H NMR of the azidoester [G-1]-(N3)6.
Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467 www.pep.wiley-vch.de D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
3 Results and Discussion
The synthesis of [G-1]-(OH)6, as shown in Scheme 1,
involved protection and deprotection of hydroxyl groups
beginning with the protection of diol group of DMPA by
acetal formation with 2,2-dimethoxy propane and catalytic
p-toluenesulfonic acid. 2,2-Dimethoxypropane was chosen
for the protection of the diol because after esterification
deprotection is facile in an acid medium, regenerating the
terminal hydroxyl functionality. During esterification, neu-
tral conditions are maintained as both the dehydrating agent
DCC and the catalyst 4-(dimethyl amino) pyridinium-p-
toluenesulfonate (DPTS) are neutral. All the reactions
involved in the synthesis of [G-1]-(N3)6 and [G-1]-(N3)8 are
high yielding with minimum impurities.
The final products as well as the intermediates involved
have been fully characterized by elemental analysis, IR, and
1
H NMR. Protection, deprotection, and substitution by N3
group were monitored by IR. 1H NMR spectra are shown in
Figures 1 and 2.
The DSC (Figures 3 and 4) and TGA thermograms
showed thermal stability up to 190 8C. DSC revealed
exothermic decomposition with Tmax at 249.3 8C and heat
release on the order of 2620 J g1 for [G-1]-(N3)6 and a Tmax
at 248.2 8C and heat release on the order of 2619 J g1 for[G-
1]-(N3)8, respectively. The glass transition temperature was
found to be  54 to  32 8C, respectively, which is sufficiently
Synthesis and Characterization of First Generation Dendritic Azidoesters 465

1
Figure 2. H NMR of the azidoester [G-1]-(N3)8.

Figure 3. DSC thermogram of the azidoester [G-1]-(N3)6.

D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467
466 C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, M. Thekkekara, S. Venugopalan

Figure 4. DSC thermogram of the azidoester [G-1]-(N3)8.

Table 1. Properties of the azidoesters [ G-1]-( N3)6 and [ G-1]-( N3)8.

Properties [G-1]-( N3)6 [ G-1]-( N3)8
DSC, Tmax (8C ) 249.3 248.2
Heat release, DH ( J g1) 2620 2619
Glass transition temperature, Tg (8C )  54.0  32
TGA, weight loss (%) 92.7 (209 – 436 8C ) 90.1 (190 – 278 8C )
Oxygen balance (%)  131.6  119.9
Heat of formation (Df HðgÞ0
) (kJ mol1) 738.3 1065.5
Impact sensitivity (cm) > 170 > 170
Friction sensitivity (kg) 36 36

low as to be suitable for application as an additive in

energetic polymer blends. As shown in Table 1, the azi-
doesters were fairly insensitive to impact and friction.
4 Conclusion
Two first generation azido-terminated dendritic esters
have been synthesized. Structural features were confirmed
by IR and 1H NMR. The azidoesters show low glass
transition temperatures, high heat release capabilities,
insensitivity toward impact and friction stimuli, and accept-
able thermal stability for their application in high energy
material formulations.
5 References
[1] A. Provatas, Energetic Polymers and Plasticizers for Explosive
Formulations – A Review of Recent Advances, Report DSTO-
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[2] D. Drees, D. Loffel, A. Messmer, K. Schmid, Synthesis and
Characterization of Azido Plasticizer, Propellants, Explos.,
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[3] J. M. J. Frechet, D. A. Tomalia, Dendrimers and Other Den-
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[4] T. J. Mulkern, N. C. B. Tan, Processing and Characterization of
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[5] J. S. Moore, S. I. Stupp, Room Temperature Polyesterification,
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[6] J. M. J. Frechet, D. A. Tomalia, Dendrimers and Other Den-
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[7] a) S. W. Benson, J. H. Buss, Additivity Rules for the Estima-
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[8] A. Lee, C. K. Law, A. Makino, Aerothermochemical Studies of
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Synthesis and Characterization of First Generation Dendritic Azidoesters 467

[9] L. Avrami, R. Hutchinson, The Sensitivity to Impact and Acknowledgement

Friction, in: H. D. Fair, R. F. Walker (Eds.), Energetic Materi-
als. Vol. 2. Technology of Inorganic Azides, Plenum Press, New The authors wish to thank Dr. A. Subhananda Rao, Director
York 1977, p. 111. HEMRL, for his guidance and for permission to publish this work.

D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467