R.A.

Rodriguez Chemistry of High Energy Materials Baran GM

2012-08-18

History of Explosives
High Energy Materials
7th century A.D.- "Greek Fire" petroleum distillate used by
Byzantines of Constantinopole

13th century - black powder (aka gunpowder) Chinese alchemists

Explosives Non-explosive materials 18th century - black powder composition became standardized:
KNO3/charcoal/sulfur (75/15/10 w/w)

19th century - NH4NO3 replacement for KNO3 in black powder

1846 - Italian Chemist Ascanio Sobrero invented nitroglycerin (NG)

High Explosives Low Explosives
1863 - German chemist Julius Wilbrand invented 2,4,6-trinitrotoluene (TNT)
[detonate] [deflagrate-burn rapidly] originally used as a yellow dye. Potential as an explosive not appreciated
due to difficulty to detonate (insensative).

1866 - Mixing of NG with silica (PBX) to make malleable paste (dynamite)

1° Explosives 2° Explosives Propellants Pyrotechnics

[detonate by ignition] [need detonator] - Black powder - Fireworks late 19th century - nitration chemistry on common materials (resins,cotton, etc.)
- Lead azide - TNT - liquid/solid - Color/flash/sound
- Tetrazene - RDX 1910 - military use of TNT for artillery shells and armour-piercing shells

1939-1945 - World War II - Research on explosives intesified (nitration chemistry)

Developlment of cyclotrimethylenetrinitramine (RDX) and
Organic Chemistry of Explosives by J.P. Agrawal and R.D. Hodgson cyclotetramethylenetetranitramine (HMX).

Prof. Thomas Klapotke - Ludwig-Maximilians-Universität München - Germany Introduction to high energy materials terminology
Chair of inorganic chemistry Brisance: Shattering capabiliy of explosive. Measure of rate an explosive
develops its maximum pressure.
Dr. Michael A. Hiskey - Los Alamos National Laboratory
Relative effectiveness factor (R.E. factor): Measurement of an explosive's
power for military purposese. It is used to compare an explosive's
What makes an explosion? effectiveness relative to TNT by weight (TNT equivalent/kg or TNTe/kg).

Exothermic chemical reaction comprised of an oxidant and fuel, which releases Detonation velocity (VoD): The velocity at which the shock wave front travels
energy (gas and heat) in a given time interval. through a detonated explosive. Difficult to measure in practice so use
gas theory to make prediction.

Whats the difference between explosive, propellants and pyrotechnics?
Rate at which it burns (Flamming gummy bear vs. rocket booster vs. TNT)
Speed of reaction will determine subsonic vs. supersonic blast pressure waves
Specific impulse (Isp): The force with respect to the amount of propellant used
per unit time. Used to calculate propulsion performance.
Oxygen balance (OB%): Expression used to indicate degree to which explosive
can be oxidized. If explosive contains just enough oxygen to form carbon
dioxide from carbon, water from hydrogen molecules and all metal oxides from
metals with no excess, the explosive is said to have zero oxygen balance.
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

Chemical types/class of organic explosives

Aromatic C-nitro compounds
Aliphatic C-nitro compounds
NO2 NO2 NO2
R2 NO2 HO
Me (NO2)x
acidic protons
R NO2 R1 NO2 R NO2 (condensation
chemistry) O2N NO2 O2N NO2 x≥4
1° nitroalkane 2° nitroalkane Terminal O2N NO2
poor chemical
gem-dinitroalkane TNT 1,3,5-trinitrobenzene 2,4,6-trinitrophenol
stability
(TNB) (picric acid)
R2 NO2
R3 R2
R2 NO2 high explosive with Aliphatic O-nitro compounds Aliphatic N-nitro compounds
R1 R1 NO2
R1 NO2 NO2 high thermal and
NO2 Internal chemical stability
O2NO ONO2 NO2 O2N NO2
3° nitroalkane Trinitromethyl gem-dinitroalkane N N
ONO2 N
NO2 Nitroglycerin (VOD=7750 m/s)
heterocycles O2NN NNO2 N N N N
NO2 ONO2 O2N NO2 O2N NO2
O2NO
RDX (VOD=8440 m/s) HMX (VOD=9110 m/s)
O2NN NNO2 O
O2N NO2 ONO2 NO2
N O2NO O2N NO2 N
H S O N N
Pentaerythritol tetranitrate H H
H2N NH2
Nitro derivatives of pyrroles, thiopenes, and furans are not practical explosives: (PETN) (VOD=8310 m/s) N,N'-dinitrourea
1. heat of formation offers no benefits over standard arylene hydrocarbons (DNU) nitroguanadine
2. during nitration, these heterocycles are much more prone to oxidation and NO2
O2NO ONO2
acid cat. ring opening compared to arenes O2N NO2
O2N NO2
H-bonding O2N O O2NO ONO2 N N
H2N NO2 NO2 O2N NO2
reduction in O2NN NNO2 N N
N novel energetic nitrate eseter
sensativity N NH
N N N
O2N N O ONO2
F2 N NF2 O2N NO2
H NO2 N O2NO
4-amino-3,5-dinitropyrazole 2,4-dinitroimidazole furazans/benzofurazans Si 3,3-bis(difluoroamino)
Hexanitrohexa-
(LLM-116) (2,4-DNI) furoxans/benzofuroxans octahydro-1,5,7,7-
ONO2 azaisowurtzitane
O2NO tetranitro-1,5-diazocine
O (HNIW or CL-20)
NH2 NH2 (TNFX)
O2N N Si-PETN (VOD=9380 m/s)
O2N NO2 O2N N NO2 O
N N N H2N H
H2N N N
N N
N N O2N O
N N
H2N N NH2 H 2N N NH2 Ar Ar Ar
O NO2 N N N O
NO2 N NH
NH2 N N
O O benzotriazoles H H 1,3,4-oxadiazoles 3-nitro-1,2,4-triazol-5-one
pyridine N-oxide pyrazine N-oxide tetrazine N-oxide tetrazoles 1,2,4 triazoles (NTO)
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

Nitration chemistry TMS NO2

AcONO2 NO2 NO2 O
The nitro gorup whether attached to aromatic or aliphatic carbon, is probably
the most widely studied of the functional groups and this is in part attributed
to its use as an 'explosophore' in many energetic materials. ONO2 ONO2
[2+2]
Borgardt et al. Chem Rev 1964. 64, 19 (polynitro functionality) _ OAc Nef
_ OAc AcONO2
Routes to C-Nitro functionality TMS NO2 NO2
O O
NO2+ O
N N N
Direct nitration of aliphatic and alicyclic hydrocarbons possible in the vapor
phase using HNO3 or NO2 (toxic redish-brown gas) at elevated temperatures. O O O OAc

H NO2 O2N NO2

HNO3 alkaline nitration
NO2 Nitration with HNO3 is difficult
25% H NO2
Me Me Me Me NO2 NO2 NO2
O2N O2N O2N O2N NO2
1. NaHMDS
Me Me N2O4 O2N NO2 O2N ONO 2. N2O4
O2N ONO2 O2N O2N O2N O2N
NO2 74% NO2 NO2 NO2
O O + +
Me Me Me Me Me Me
Me Me N N Me Me Me Me Me Me
O O dinitro nitro-nitrite nitro-nitrate Br NO2
1. nBuLi
- colorless liquid
2. N2O4 -78 °C
S S
Radical methods 77%
OH O2N Cl
1 atm NO NO2 NItration selectivity on arene/heteroarene
+
NO2
Ph Ph Ph Kakiuchi, et al. Synlett 1999. 901 N
DCE/ rt KNO3
76% 23%
Al2O3 H2SO4
Cl traditional N
NO2 [NO2+]
Mukaiyama et al. Chem Lett 1995. 505 Ph CO2R
92% N 44%
NaNO3 xs,
H H H NO2 R Fe(NO3)3 9H2O R Cl
CAN 2eq
FeCl3 Cl
R R AcOH/CHCl3 N
R R MeCN, reflx
R R NO2 N
80 - 90% CO2R TBAN NO2
80 - 90%
H NO2 H NO2 TFAA
NO2BF4 NHAc O O TBAN O * No rxn in
H Ph
76% presence of
H NO2 N
R R R R MeCN NO2 TEMPO
Ph F3 C O CF3 F3C O
84% CO2R
Hwu et al. J Chem Soc Chem Commun 1994. 1425
Taniguchi et al. JOC 2010. 75, 8126
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

1° and 2° nitro compounds O NOH NO2

CF3CO3H O OH
Victor Meyer rxn N only useful
- alkyl chlorides too slow oxidant
- only good for 1° (2° alkyl halide gives nitrate ester) 1.KOtBu
1. NBS
- nitrate ester arises from desproportionation of silver nitrate acc. by heat/light amyl nitrate NO2+
2. [O]
2. H+ S2O8 2-
O 3. [H] O2N NO2
+
N ether
+ AgX NO O O O H+
R X R NO2 R O O2N NO2
OAg NO2 N
NO2H
NO2+ O2N NO2
modified VM (alkali metal nitrites e.g. NaNO2) time and solubility is VIMP
(low yields) Kaplan
R NaNO2 R R N O NaNO R NO R Shechter Rxn
DMSO NO2 + O
2
NO2 OH
X
fast slow NO2
R R R nitrite ester R R Synthesis of an energetic nitrate ester O2NO ONO2
O
H+ OH
O N Chavez, D.E. et al. Angew. 2008, 47, 8307 O2NO ONO2
R OR NO2
NO2 HO OH O
O O O
R phloroglucinol NO2 NaOH N 1. NaNO2 O2N NO2 Ag0
Kornblum et al. JACS 1956. 78, 1497
Fluorotrinitromethane 2. AgNO3 Ag+
R1 R2 R1 R2 R1 R2
NO2 nitronate
NO2 NO2 NO2 Ag
NO2 (or) NO2 O O Ag+ O O
N -Ag0 O O
O2N NO2 F NO2 F NO2 O O
O N N O N N O
N N O O
R2 O
gem-dinitros from acids R1
R1 R2 R1 R2
O R1 R2
R N
R NO2 NO2
HNO3 HNO3
CO2H O Na
MeO2C CO2H Original Target/Route via modified Kaplan Shechter Rxn
R 20 - 30% R NO2 60 % MeO2C NO2
NO2 retro
Me O Me O O aldol Me O NO2
oxidation of amines
Me NH Me N Me
NH3+Cl- NO2 -CH2O
O NH O O O OH
DMDO N N
Acetone N
C+H3N O2N Fe
NH3+C 91% NO2
C+H3N O2N O O O O O O
N activation N [O] N
Me O Me O R
oxidation of isocyanates
Me NH Me NH NH
NCO NO2 via amine thus
H2O essential O NH O R NH
DMDO NH
N N N N N
Acetone/H2O Eaton et al. JOC 1988. 5353 N N
O2N N N
OCN
85%
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

Initial Results: homocoupled product

Routes to O-Nitro functionality
1. 2-methoxypropene 1.cat. K3[Fe(CN)6]
HO NO2 cat. H+ Me O O Na2S2O8 - Use of mixed acids (esterification) and nitrogen oxides described for C-Nitraion
Me N H Key points:
2. NaOH
HO OH O O N 1. fuming (anhydrous) HNO3 prep: dry air bubbled through anhydrous HNO3 to
H2N
N X remove any oxides of nitrogen present, followed by addition of trace urea
NO2 N N to remove any nitrous acid present. AKA "white nitric acid"
Me O O N
N N
2. Urea destruction of nitrous acid important to avoid violent fume-off
O O O O Me Me NO2 NH 3. O-nitrations with mixed acids of "white nitric acid" above ambient temperatures
Me O
N N O O Me
NO2 Me NH is dangerous and has increase risk of explosion
12% 4. anhydrous HNO3/Ac2O- Acetyl nitrate is generally a weak nitrating agent but
O
in the presence of a strong acid like HNO3, ionization to nitronium ion occurs
O O O O NO2 NO2 NO2
Me Me O O O2NO ONO2 anh HNO3 HO
Me Me OH 90% HNO3 HO ONO2
O O N
N Me O O Ac2O Ac2O
Me O O
activation Me Me
Me Me O2NO ONO2 90% HO OH 70% O2NO OH
O O Me
- CN- O
N
O Me N NO2 NO2 NO2
O O shock sensative
O O
NC CN NaO3S
NC CN Fe Transfer nitration (neutral conditions - good for acid sensative alcohols)
NC Fe CN +CN- O O
Me
NC Fe OSO3Na
NC CN -NaSO4- SO3Na
NC CN
BF4-
Me
NO2 NO2 Me N Me Olah G.A. et al JOC, 1965. 30, 3373
O2NO ONO2 1.HCl, MeOH Me O O OH ONO2
m.p. 86 °C
Me Me 2 eq NO2
Det.Temp + BF4-
2. Ac2O/HNO3 MeCN works for 1°, 2°, 3° alcohols
140 °C O2NO ONO2 O O Me Me N Me
NO2 NO2 OH ONO2
quant yield H
72% (2 steps)
65% optimized
in situ halide displacement with AgNO3
ONO2 Low yields for 2°
O2NO PPh3, I2 AgNO3 HgNO3 can be used for 2° and
R OH R I R ONO2 3° alkyl halide displacements
ONO2
O2NO decomposition of nitrocarbonates (very mild, rt or reflux MeCN)
comparable
stability to PETN O AgNO3 O -AgCl
R ONO2
O2N NO2 RO Cl Py RO ONO2 -CO2 80%
N N
ring opening of strained oxygen heterocycles H2O HO
N N N2O4 ONO2
20,164 MPH!! O2N NO2 O (or)
ONO
CH2Cl2 ONO2
CHEETAH calculates [O] O2NO
as powerful as HMX O ONO2
N2O5
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

selective O-nitrations
1 eq SOCl(NO3) HO ONO2 -chloride ion catalysis
65% OH anhydrous ZnCl2, hydrochloride salt of amine, or dissolved HCl(g) can serve
HO OH 2 eq SOCl(NO3) O2NO ONO2 as a source of electropositive chloride under the oxidizing conditions of nitration
OH 70% OH
3 eq SOCl(NO3) O2NO 2 HCl + 2HNO3 + 3Ac2O 2AcOCl + N2O3 + 4AcOH
ONO2
100% ONO2 AcOCl + R2NH R2NCl + AcOH
nitrodesilylation deamination R2NCl + HNO3 + Ac2O R2NNO2 + AcOCl + AcOH
N2O5
RO SiR3 RO ONO2 + O2NO SiR3 NO2F
CH2Cl2 R NH2 R ONO2 Wright et al. Can. J. Res. 1948. 26B, 294
MeCN
NO2
Routes to N-Nitro functionality NC N CN HNO3/Ac2O NO2
R = Cl- (N+)
- Compounds resulting from nitration of nitrogen are of far less use for 93% R N
NC CN
mainstream organic synthesis. However the N-NO2 group is an important HNO3/Ac2O N HNO3/Ac2O 70%
'explosophore' and is present in many enrgetic materials (w/o chloride) NC CN R=H
- Direct nitration of a 1° amine to a nitramine using HNO3/mixed acids is not X
possible due to instability of the tautomeric isonitramine in strongly acidic
conditions. 2° amines are more stable and can undergo electrophilic nitration NO2 NaHSO (aq)
2 HOCl HNO3/Ac2O 3
using HNO3/Ac2O R NH2 R NCl2 R N R NHNO2
NO2
2° w/ HNO3/Ac2O Cl
O N NO2
OH NO2 - Nitrolysis of fully substituted nitrogen
HN N
H+ N
N N R OH + N2O NC N CN Me Me rupture of C−N bond leading to formation on N−NO2
R O R O
93% 22% 6%
O2N R2
A Path A N
analines - must contain one or more nitro groups on the aromatic ring + R1 CO2H
O
R2
How to get around this problem?? R2
- synthesis via condensation chemistry (Mannich, 1,4 addition, etc) R1 N O
R2 Path B NO2
What about if need more direct method?? R1 N + R2 OH
-non-acidic nitrating reagents (nucleophilic nitration) B
R2
O NO2 Nitramine formation via nitrolysis possible from:
nBuLi Et ONO2 H+
R NH2 R N N R NH
R NHLi
-78 °C R1 R1 - carbamate
OLi NO2+ NO2
O
- urea
N N R2N NR2 R2N SiR3
R1 R2 - formamide
R1 R1 N
1. Na - O H+ NO2
Ph R2N NO - acetamide
Ar NH2 Ph R2 - sulfonamide
Ar NH2 Na+ Ar N N Ar NH
2. EtONO2 EtONO2
ONa Ease of alkyl nitrolysis depends on stability of the resulting cation:
benzyl, tertiary (t-Bu), etc...
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

Synthesis of Hexanitrohexaazaisowurtzitane (HNIW)

Syntheses of some nitramine explosives
- Many nitramines are more powerful than aromatic C-nitro compounds and have 1. CrO3, AcOH NNs NNs
NH2 NH2 NsCl, NNs NNs
high brisance and high chemical stability and low sensativity to impact and 2. HOCH2CH2OH
friction compared to nitrate ester explosives. This is why they are of interest to K2CO3 (aq) TsOH
military applications. 82% (2 steps) O O
Bn 95%
Bn Bn Bn OH OH
O Bn
NH2 N N N N N
MeCN/H2O Bn Bn
H N N Br Br 76%
+ H
Ph cat. H+ K2CO3
N N N N
O N NOH
2 eq. Bn Bn Bn Bn O2N NO2
Bn
H2, 1. HNO3/NH4NO3 1. O3, CH2Cl2
O
Ph
[O] Ph Me [Pd] X X NO2+ NNs
urea, 33%
NNs
2. DMS
Ac2O NNs NNs NNs NNs
O 2. H2SO4
N 3. NH2OH/NaOAc
N N
92% 86% (3 steps)
decomp. messy. Nitration O O
of aromatic rings O O
O
Ph O
CrO3 Ph
N
N F2NSO3H,
90% HNF2, H2SO4,
Bn Ac O2N Ac NO2 O2N NO2 O2N NO2
Bn 1. N2O4 CFCl3
N N N N N N
Bn
N
Bn H , Pd(OAc) Ac Ac 2. HNO3/H2SO4 2N
O
N NO2 HNO3/SbF6
N 2 2 N N N
Ns N N Ns O2N N N NO2
Ac2O, PhBr cat. via nitroso CF3SO3H
N N N N 93% N N
Bn Bn 65% Bn Bn DANGER! O2N NO2
H2, F2 N NF2 F2N NF2
O2N NO2 [Pd] 99% HNO3
TNFX
N N
O2N Ac Ac (3,3 bis(difluoroamino)octahydro
N N NO2 Ac Ac
N N 1. HCO2H N N 1,5,7,7 tetranitro 1,5 diazocine)
Ac Ac Ac Ac
N N N N N N
O2N NO2 2. Ph, Δ
NH2 NH3+Br- Br
HN NH -H2O OHCN NCHO 1. NaNO2 (aq)
HNIW aka CL-20 HO OH HBr-AcOH Br Br
NaOH, 80 °C
2. HCl (aq)
- explosive/propellant (low smoke-emission) 160 °C 60 mmHg
- most powerful to date (better oxidizer-to-fuel than RDX/HMX) OH 72% 10%
Br N
- first prep by Nielsen 1987 Naval Air Warefare
- pilot plant in 1990 for 200 kg in China Lake facility
O2N NO2
- unmatched performance in specific impulse, 1. NaHCO3, NaI O2N CH2Br O2N CH2Br
burn rate, detonation velocity (9.38 km/s = 21,000 MPH!!) DMSO, 100 °C HNO3/TFAA
- highest density than any other explosive (d = 2.044 g/cm3) N
2. NaNO2, NaOH N 81% N
- thermally stable (250 -260 °C) but sensative to mechanical stress NO2 K3Fe(CN)6, K2S2O8 NO2
still greater stability than nitrocellulose, PETN and others. TNAZ NO
29% (2 steps)
- 4 different polymprphs with different densities/properties
 R.A. Rodriguez Chemistry of High Energy Materials Baran GM
2012-08-18

N2O5 No single nitrating agent is as diverse and versatile Preparation of N2O5 [Deville 1849] O
It is considered as the future for energetic materials synthesis
AgNO3 + Cl2 (g) N + AgNO3 N2O5
non-acidic nitrating reagents (neutral) O Cl
1° amines/nitramines leads to deamination and formation of nitrate ester Dehydration of nitric acid
by-product but analines are successful. HNO3 + P2O5 N2O5 + H3PO4
O O nitronium nitrate salt O3
- adopts two structures Δ
N2O5 N N [NO2+][NO3-] N2O4 N2O5
O O O depending on condition
- isolation by sublimation and collection trap at -78 °C
sublime slightly above rt polar - stream of ozone needed to avoid collection on N2O4
condition: chlorinated solvents condition: anhyd. HNO3 - if don't care about acidity, can use HNO3/P2O5 mixture directly (no ozone stream)
- clean and selective - powerful but acidic and non-selective
- non-oxidizing &n non-acidic Process chemist at Defense and Evaluation Research Agency (DERA) in the UK
Development of a flow process: Using commercial ozonizer to generate 5 - 10%
- 1st prepared over 150 years ago but due to difficult prep and low thermal mix of ozone in oxygen and mixed in flow with N2O4. N2O5 is trapped in solid
stability (require -60 °C long term storage) received little attention. condenser tubes (cooled by dry ice/acetone).
- Environmental restrictions and push for green chemistry sparked interest
Explosives in JACS: Sila explosives
Klapotke T.M. JACS 2007. 129, 6908
Advantage: Rxns are very clean O2NO
- faster and less exothermic (due to absence of oxidation byproducts) - Used in WW I
- high yields - One of most high energy explosives known
O2NO ONO2
- simple isolation - more shock sensative than TNT. used as booster mix
- non-acidic conditions possible with this reagent (compared to mixed acids) - Europe marketed as lentonitrat (vasodilator) like NG
PETN ONO2
rt Stable for 2 weeks at -20 °C
N2O5 2 N2O4 + O2 - Det. Velocity 8,400 m/s
Stable for up to 1 yr at -60 °C
- d= 1.7 g/cm3 "The crystalline compound exploded on every
synthesis of TNT under mild conditions occasion upon contact with Teflon spatula...
Silicon analogue of PETN
Me Me Solutions in diethyl ether exploded upon the slighest
VERY high e- evaporation of the solvent."
NO2 O2N NO2 O2NO dens
N2O5/HNO3
No explosion hazard
32 °C, O2NO Si ONO2 Si(CH2OAc)4 Si(CH2Cl)4
quant yield VERY
NO2 NO2 ONO2
low e- dens Why does Si-PETN have drastically increased sensativity?
N-nitrations of ureas
O2N O2N NO2 Theoretical: electrostatic potential:
H H H 1. Surface electrostatic potential, in general, is related to the sensitivity of the bulk
N N N N N N
HNO3 HNO3 2. The more evenly distributed the electrostatic potential is over the surface of a
O O O O O O
H2SO4 P2O5 molecule, the more stable it is to impact.
N N N N N N
H H H
NO2 O2N NO2 O2NO O
O-nitrations of polyols
OH OH ONO2 ONO2 N O
O2NO Si
N2O5, CCl4 O
OH ONO2
HO 0 °C O2NO
O2NO
OH OH quant yield ONO2 ONO2