REFERENCES Ejm
1. V. P. Iushin, M. S. Komelin and V. A. Tartakovsky, Zh. Org. Khim., 1999, 35, 489. 2. R. D. Chapman, J. W. Fischer, R. A. Hollins, C. K. Lowe-Ma and R. A. Nissan, J. Org. Chem., 1996, 61, 9340. 3. J. O. Doali, R. A. Fifer, D. I. Kruezynski and B. J. Nelson, Technical Report No. BRL-MR-378 5, US Ballistic Research Laboratory, MD 1989 . 4. T. G. Archibald, K. Baum, C. George and R. Gilardi, J. Org. Chem, 1990, 55, 2920. 5. T. G. Archibald, S. G. Bott, A. P. Marchand and D. Rajagopal, J. Org....
References
1. a T. Urbanski, Chemistry and Technology of Explosives, Vol. 1, Pergamon Press, Oxford 1964 b T. Urbanski, Chemistry and Technology of Explosives, Vol. 4, Pergamon Press, Oxford 1984 c Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edn, Vol. 10, Ed. M. Grayson, Wiley-Interscience, New York, 1-125 1993 . 2. N. Ono, The Nitro Group in Organic Synthesis., Organic Nitro Chemistry Series., Wiley-VCH, Weinheim, Chapter 2, 3-29 2001 . 3. G. A. Olah, R. Malhotra and S. C. Narang, Nitration...
Transfer nitration
Olah and co-workers50-53 conducted a comprehensive study into the use of N-nitropyridinium salts for nitration. Such salts are easily prepared from the slow addition of the appropriate heterocyclic base to an equimolar suspension of nitronium tetrafluoroborate in acetonitrile. Olah studied the effect on nitration of changing both the structure of the heterocyclic base and the counter ion. Three of these salts 20, 21, 22 illustrated above have been synthesized and used for the O-nitration of...
REFERENCES Qrs
1. I. J. Dagley and R. J. Spear, in Organic Energetic Compounds, Ed. P. L. Marinkas, Nova Science Publishers Inc., New York, Chapter 2, 135 1996 . 2. The Chemistry oftheAzido Group, Ed. S. Patai, Interscience, London-New York 1971 . 3. M. B. Frankel, E. R. Wilson and D. O. Woolery, 'Energetic Azido Compounds', Ann. Rep. AD-A083770 1980 . 4. M. B. Frankel and E. R. Wilson, US Pat. 4 499 723 1985 , Chem. Abstr., 1985, 103, 8576h. 5. J. E. Flanagan, M. B. Frankel, E. R. Wilson and E. F. Witucki,...
REFERENCES Yyo
1. a T. Urbanski, Chemistry and Technology of Explosives, Vol. 2, Pergamon Press, Oxford 1965 b T. Urbanski, Chemistry and Technology of Explosives, Vol. 4, Pergamon Press, Oxford, Chapter 10 1984 c V. Linder, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edn, Vol. 9, Ed. M. Grayson, Wiley-Interscience, New York 1980 . 2. a E. H. Zeigler, European Pat. 66 999 1982 b G. Doriath, J. Propulsion Power, 1995, 4, 870 c M. L. Chan, US Pat. 5 316 600 1994 . 3. Encyclopedia of Explosives and...
Primary Nitramines As Nucleophiles
Primary nitramines contain an acidic proton which enables them to behave as nucleophiles and undergo addition and condensation reactions. These reactions are extremely useful in two respects. Firstly, these reactions convert primary nitramino functionality into secondary nitramino functionality, which is no longer acidic and much more chemically stable. Secondly, these addition and condensation reactions can be used to prepare functionalized derivatives of polynitramines which can be used to...
Info Wdj
The nitrogen atoms of heterocycles like imidazoles and triazoles have been converted into N-nitroimide groups. The N-nitroimide 164 is synthesized from 1-amino-1,3,4-triazole 162 by N-amination of the tertiary nitrogen with O -picrylhydroxylamine, addition of nitric acid to give the nitrate salt 163 , followed by N-nitration with nitronium tetrafluoroborate in acetonitrile.90 The 1,2,3-triazole 165 91 and the imidazole 166 90 are synthesized in a similar way. The synthesis of N-nitroimides has...
MEMBERED RINGS N Pyrazoles
Heat of formation and density calculations correlate so well with performance parameter like detonation velocity that chemists have a good idea of the performance of an energetic material before its synthesis and testing. The pyrazolo 4,3-c pyrazoles DNPP 9 and LLM-119 10 were predicted2 to exhibit performances equal to 85 and 104 relative to that of HMX. Shevelev and co-workers6 first synthesized DNPP 9 from 3,5-dimethylpyrazole. Subsequently, Pagoria and co-workers7 improved the synthesis,...
Info Dga
Highly nitrated derivatives of cubane are prepared by treating the anion s of 1,3,5,7-tetranitrocubane 39 with dinitrogen tetroxide in frozen THF.1014 Anion formation requires the use of a relatively strong base, namely, sodium hexamethyldisilazide, a consequence of proton removal from a carbon i to the nitro group. This is not normally possible, but in this special case three electron-withdrawing nitro groups flank each i -proton and the strained cubane core causes deviation from sp3...
Info Mkv
Some energetic compounds are engineered to contain two or more different energetic functionalities. The azido group has a high heat of formation and so its presence in energetic materials is favorable on thermodynamic grounds. However, compounds containing only the azido 'explosophore' rarely find use as practical explosives. More common is the incorporation of other functionality into such compounds. In the case of 130 AZTC , an azido derivative of HMX, the azidomethyl group triggers initial...
H H
The reaction of 2-fluoro-2,2-dinitroethanol 119 with divinylether 118 under different conditions gives three products, namely, the expected vinyl acetal 120 and the bis-acetal 121 from addition of one and two equivalents of 2-fluoro-2,2-dinitroethanol, respectively, and the vinyl ether 122 , which results from trans-etherification of 118 with loss of acetaldehyde. Shackelford and co-workers246 found that by altering the nature of the Lewis acid catalyst and the reaction stoichiometry they were...
Fox
furazan-piperazine fused ring systems 301 furazan-based heterocycles, N-nitration of 197-8, nitro and amino derivatives 297-302 nitro-substituted 298-9 picrylamino-substituted 299 furoxans, nitro derivatives 302-3 gelatinized explosives 87, 89 gem-dimethyl effect 197 glycerol 90 glyceryl dinitrate, synthesis 97 glyceryl nitrate, synthesis 97 glyceryl trinitrate GTN 87-8 see also nitroglycerine glycidyl azide polymers GAP 337 glycidyl nitrate GLYN 98, 116, 362-3 guanidine nitro derivatives 192,...
NO Vzf
Phloroglucinol 25 is more susceptible to oxidation than both phenol and resorcinol. However, its direct nitration to 2,4,6-trinitrophloroglucinol 27 can be achieved by the slow addition of a nitrating agent composed of concentrated sulfuric acid and concentrated nitric acid to a solution of phloroglucinol dihydrate in concentrated sulfuric acid between 0 and 10 C 72 .28-30 Acetylation of phloroglucinol 25 yields the triacetate 26 which moderates reactivity but still allows the synthesis of...
Info Eme
Chemists at Lawrence Livermore National Laboratory LLNL synthesized the RDX analogue 125 Keto-RDX or K-6 from aMannich reaction between urea, formaldehyde and t-butylamine, followed by nitrolysis of the resulting 2-oxo-5-tert-butyltriazone 124 with nitric acid in acetic anhydride or dinitrogen pentoxide in absolute nitric acid.20'21 Nitrolysis with other nitrating agents has also been reported, including nitronium tetrafluoroborate 40 , TFAA-nitric acid 43 and mixed acid 0 -see Table 5.6.21'49...
Benzotriazoles
BTX 145 was first synthesized by Coburn and coworkers91 from the reaction of benzotriazole with picryl chloride in DMF, followed by nitration with mixed acid. Gilardi and co-workers92 reported an alternative synthesis of BTX involving treatment of 2-amino-4,6-dinitrodiphenylamine 143 with a solution of nitrous acid, which leads to an intramolecular cyclisation via the diazonium salt to give 144 , nitration of the
Imidazoles
The direct nitration of imidazole with acidic reagents is difficult due to facile nitrogen protonation p aH 7 . Nitration of imidazoles proceeds in the 4- and 5-positions with the amidine 2-position being quite inert. Imidazole can be directly nitrated to 4,5-dinitroimidazole but no further.12 2,4,5-Trinitroimidazole TNI can be prepared from the successive nitration of 2-nitroimidazole the latter synthesized from the diazotization of 2-aminoimidazole in the presence of excess sodium nitrite and...
Info Vmp
A number of energetic polymers containing nitrate ester functionality have received attention for use as binders in high performance propellant and explosive formulations. Nitrated hydroxy-terminated polybutadiene 121 NHTPB is synthesized from the epoxidation of the double bonds of HTPB 120 oligomers with peroxyacetic acid, followed by ring-opening nitration of the resulting epoxide functionality with dinitrogen pentoxide in methylene chloride.76 Nitrated HTPB with 10 of the double bonds...
Caged Structures As Energetic Materials
Many explosives in frequent use today derive their energy solely from the heat released on the combustion of the carbon skeleton. Considerable research efforts have focused on synthesizing explosives containing strained or caged structures which derive their energy from both the heat of combustion of the carbon skeleton and the relief of molecular strain. Energetic materials with caged structures also benefit from a decrease in molecular motion which often leads to higher crystal density and a...
N Dnw
Poullain and co-workers10 synthesized by treating substituted pyrimidines with N-alkylhydrazines. 3,5-Diamino-4-nitropyrazole 14 has been synthesized by treating the pyrimidine 13 with hydrazine hydrate. This methodology is limited in scope but the products are useful intermediates for the synthesis of insensitive high explosives.
NO ON Jzz
2,2',4,4',6,6'-hexanitrocarbanilide 2,4,6-Trinitrophenol 4 , commonly known as picric acid VOD 7350 m s, d 1.71 g cm3 , was once used as a military explosive although its highly acidic nature enables it to readily corrode metals. This kind of reaction has led to many fatal accidents, a consequence of some metal picrates being very sensitive primary explosives. The lead salt of picric acid is a dangerous explosive and should be avoided at all cost. In contrast, the ammonium Explosive D, VOD 7050...
With 40 Equivalents Of A 25 Solution Of Dinitrogen Pentoxide
This unusual process known as the W-method was discovered in Germany by Wolfram201 and involves the condensation of the potassium salt of sulfamic acid with formaldehyde to form the heterocycle 238 followed by treatment with nitric acid. The extreme sensitivity of 238 to hydrolysis means that nitrolysis has to be conducted under anhydrous conditions using sulfur trioxide201 or phosphorous pentoxide204 dissolved in fuming nitric acid. The yield of RDX from the W-method is 80-90 . 5.15.1.6...
ON Qrj
Highly nitrated derivatives of benzene readily react with water to form phenols. 1,2,3,5-Tetranitrobenzene 54 is readily converted to picric acid on reaction with hot water.252 This type of reaction has practical concerns if such an explosive is used in a military context -picric acid forms dangerous picrates if allowed to come into contact with a metal surface i.e. the inside of a munition's shell. Other explosives like 2,3,4,6-tetranitrophenol 121 and 2,3,4,6-tetranitrotoluene react with...
Adamantanes
The highly rigid skeleton of adamantane results in much higher crystal densities compared to its open chain counterparts, and hence, higher performance for its nitro derivatives. The adamantane core shows little to almost no strain and so some of its polynitro derivatives show exceptionally high thermal stability. Research has focused on placing nitro groups on the tertiary carbon bridgehead positions of adamantane, and forming gem-dinitro derivatives at the methylene carbon positions. Both...
Info Vaz
Boyer and co-workers87 used a solution of nitronium tetrafluoroborate in acetonitrile for the introduction of the final nitro group into the energetic dinitrourea 75 . A number of reagents derived from nitrate salts and acid anhydrides have been reported for the N-nitration of amides and related compounds. Crivello88 first reported the use of metal nitrates in trifluoroacetic anhydride TFAA for the nitration of aromatic systems. Chapman and Suri89 used the same system, which probably involves...
Info Wah
3,3-Bis azidomethyl oxetane BAMO 28 , the product from treating 3,3-bis chloromethyl oxetane 27 with sodium azide in DMF,19 undergoes acid-catalyzed ring opening on reaction with 70 nitric acid to give the nitrate ester 29 .20 Treatment of 29 with nitric acid in acetic anhydride yields 2,2-bis azidomethyl -1,3-propanediol dinitrate PDADN 31 .20 Reaction of BAMO 28 with aqueous hydrobromic acid in methylene chloride, followed by treatment of the resulting bromide with sodium azide in DMSO,...
Info Kbi
Azido groups are conveniently incorporated into aromatic rings via nucleophilic aromatic substitution of aryl halides containing nitro or other deactivating groups o p- to the leaving group. 1,3,5-Triazido-2,4,6-trinitrobenzene 40 , the product from the reaction of 1,3,5-trichloro-2,4,6-trinitrobenzene with excess sodium azide, is an explosive with VOD 7500 m s at d 1. 54 g cm3 and has some prospects of practical use as a primary explosive.31 Cyanuric triazide 41 , prepared from cyanuric...
Direct Nitration Of Alkanes
Nitroalkanes can be formed from the direct nitration of aliphatic and alicyclic hydrocarbons with either nitric acid10 or nitrogen dioxide11 in the vapour phase at elevated temperature. These reactions have achieved industrial importance but are of no value for the synthesis of nitroalkanes on a laboratory scale, although experiments have been conducted on a small scale in sealed tubes.12-14 The vapour phase nitration of hydrocarbons proceeds via a radical mechanism3-15 and so it is found that...
Diazophenols
Diazophenols, also known as diazo oxides or diazonium phenolates, are thought to be zwitterions40 with negative and positive charges localized on the oxo and diazo groups respectively, although tautomeric quinonoid41 structures have not been ruled out. Most diazophenols are sensitive to impact and exhibit properties which are characteristic of primary explosives, the nitro derivatives exploding violently on the application of heat or mechanical stimuli. Studies of these compounds have focused...
Oxidation of nitrosoalkanes
Nitroso compounds are formed during the addition of nitrous oxide,48'49 dinitrogen trioxide,48'49 and nitrosyl halides50 to alkenes, and in some cases, from incomplete oxidation of amines166 with peroxyacids like peroxyacetic acid. Quenching of carbanions with nitrosyl halides is also a route to nitroso compounds.190 A full discussion on this subject is beyond the scope of this work and so the readers are directed to the work of Boyer.191 Oxidation of aliphatic nitroso functionality is usually...
Nucleophilic Aromatic Substitution
The nitro group is one of the most potent substituents for withdrawing electron density from the aromatic nucleus. While such groups make electrophilic substitution more difficult they facilitate nucleophilic attack on the aromatic ring. Nitro groups introduce centres of low electron density at the o- and p-positions on the benzene ring, and consequently, halogens and other leaving groups in these positions are especially susceptible to nucleophilic attack. The effect of leaving group...
The Chemistry Of Dinitrogen Pentoxide
Dinitrogen pentoxide is a colorless crystalline solid which sublimes without melting at 32.5 C at atmospheric pressure.4 Dinitrogen pentoxide is inherently unstable and readily decomposes to oxygen and dinitrogen tetroxide at room temperature as shown in Equation 9.1 . The rate of decomposition is temperature dependent with a half-life of 10 days at 0 C and 10 hours at 20 C.4 9 It is stable for 2 weeks at -20 C and up to 1 year at temperatures below -60 C. Dinitrogen pentoxide is readily...
NO ON Cei
2,2',4,4',6,6'-hexanitrostilbene HNS BTDAONAB Interest in polynitroarylenes has resumed over the past few decades as the demand for thermally stable explosives with a low sensitivity to impact has increased. This is mainly due to advances in military weapons technology but also for thermally demanding commercial applications i.e. oil well exploration, space programmes etc. Explosives like 1,3-diamino-2,4,6-trinitrobenzene DATB 13 , 1,3,5-triamino-2,4,6-trinitrobenzene TATB 14 , DIPAM 15 ,...
Ter Meer Reaction
The Ter Meer reaction has been used for the synthesis of the potassium salt of dinitromethane 18 by treating chloronitromethane 17 with potassium nitrite in aqueous sodium hydroxide solution.104 The potassium salt of dinitromethane is a dangerous shock sensitive explosive and should not be isolated treatment of 18 with formaldehyde in acidic solution forms the more manageable bis-methylol derivative, 2,2-dinitro-1,3-propanediol 19 .104 Partial hydrolysis of 19 with potassium hydroxide, followed...
Effect of nitrating agent and reaction conditions on product selectivity
The nature of the substituents presence in an aromatic substrate has a large effect on which positions are substituted on nitration. The isomeric ratio of products obtained on nitration is also dependent on the nitration conditions, nitrating agent, nitrating medium and its acidity, acid composition and concentration etc., but often to a lesser extent. Substrates containing substituents with nonbonding electrons localized on heteroatoms i.e. phenol ethers, anilines, substituted anilines,...
Tnpdu Explosive
I I 2 I 82 - see fexf I I 2 I HN-CH-NH N-CH-J Tetranitropropanediurea 127 TNPDU is a high performance N,N'-dinitrourea explosive VOD 9030 m s synthesized from the nitration of propanediurea 126 with nitric acid in acetic anhydride,50 the latter readily synthesized from the condensation of urea with 1,1,3,3-tetraethoxypropane. Agrawal and co-workers46 conducted extensive studies into the synthesis, characterization and thermal behaviour of TNPDU. The nitration step was significantly improved by...
MEMBERED RINGS N Qwf
Pyrazine and pyrimidine heterocycles, like pyridine, are electron deficient and need the presence of an activating electron-releasing group to allow efficient electrophilic nitration to occur. An example of this strategy is seen during the synthesis of 2,6-diamino-3,5-dinitropyrazine ANPz 183 where one of the chloro groups of 2,6-dichloropyrazine 180 is substituted for a methoxy group which then allows nitration in the 3- and 5-positions under moderate conditions to yield 182 , nucleophilic...
Info Mop
acid at 80 C,172 more concentrated nitric acid at lower temperature,173 mixed acid174 and a mixture of nitric acid in acetic anhydride.175 Studies have shown that the nitration of N,N-dimethylaniline with mixed acid proceeds in five steps - N, N-dimethylaniline 90 first undergoes aromatic ring nitration to 227 , followed by oxidation of one of the methylamino groups to a carbamic acid group which subsequently loses carbon dioxide to form 228 , further nitration now generates nitramine 229 which...
Nitrations With Dinitrogen Pentoxide
Dinitrogen pentoxide was first prepared6 over 150 years ago but received little attention as a nitrating agent. This is probably due to technical difficulties in preparation and its low thermal stability, requiring temperatures of -60 C for its long term storage.4 Its real potential for the synthesis of polynitroarylenes, nitramines and nitrate esters, has only recently been recognized.3 5 This is in large due to sustained research at the Defence Evaluation and Research Agency DERA in the UK....
H Qcm
hydrochloride with formic acid.81-83 The facile synthesis of NTO from readily available starting materials, coupled with its high performance VOD 8510 m s, d 1.91 g cm3 , and properties which classify it as an insensitive high explosive IHE , makes NTO a very attractive explosive for use in insensitive munitions, either cast, pressed or in a plastic bonded matrix. NTO is much less sensitive to impact than both the widely used military explosives RDX and HMX.84 The French first used NTO in...
ON Mge
Recently, TATB 14 has been synthesized by treating TNB and picramide 53 with VNS aminating agents like 4-amino-1,2,4-triazole ATA and 1,1,1-trimethylhydrazinium iodide TMHI in the presence of sodium methoxide in DMSO.37'283 Hydroxylamine has been used but requires elevated temperatures for the same reaction. The main advantage of these methods is the reduction in the production cost of TATB as a result of relatively inexpensive starting materials i.e. picramide from Explosive D and TMHI from...
Introduction 1
The nitration of aromatic hydrocarbons is one of the most widely studied and well-documented reactions in organic chemistry. Aromatic nitro compounds are of huge industrial importance in the synthesis of pharmaceutical drugs, agrochemicals, polymers, solvents and perfumes, and for the synthesis of other industrially important chemicals containing amine and isocyanate functionality. However, early research into aromatic nitration was fuelled exclusively by their use as explosives and...
Polynitroarylenes As Explosives
Polynitroarylenes hold a central position in the field of explosives and for many years they have been an important class of explosives for military use. 2,4,6-Trinitrotoluene TNT 1 was first synthesized in 1863 and has found wide use as a secondary high explosive. It is by no means a high performance explosive VOD 6940 m s, d 1.64 g cm3 , but it has a combination of properties, such as relatively high chemical stability, moderate insensitivity to impact and friction, and a low enough melting...
Info Jfa
the carbon chain give much lower yields of nitro compound.64 Reactions with such substrates are much slower and nitrite ester formation is much more of a problem. In fact, the nitrite ester and the corresponding alkene can be the main products of the reaction of a secondary alkyl halide with silver nitrite. Consequently, the Victor Meyer reaction is not considered useful for the synthesis of secondary nitroalkanes. Nitrate ester by-products72'73 can arise from either disproportionate of silver...
Nitration
The direct nitration of aromatic substrates is usually the method of choice for the synthesis of aromatic nitro compounds on both industrial and laboratory scales. Other routes are usually only considered when the required product has an unusual substitution pattern or is so deactivated that nitration is exceptionally difficult. Many of these alternative methods are limited to a laboratory scale. Olah1 showed that nitrations can be split into the three categories of electrophilic, nucle-ophilic...
Info Laz
of the 1,2,3,4-tetrazine-1,3-dioxide ring system starts from 215 and utilizes the reaction of the tert-butyl-NNO-azoxy group with an adjacent amino group in the presence of dinitrogen pentoxide. The tert-butyl-NNO-azoxy groups of 215 are introduced by treating the corresponding nitroso derivative with N,N-dibromo-tert-butylamine. Tartakovsky and Churakov134 recently reviewed the chemistry of 1,2,3,4-tetrazines.
NN Mhy
The tetrazole ring can be synthesized from the 1,3-dipolar cycloaddition of an azide with a cyanide group or a similar nitrogen dipolarophile. Tri-n-butyltin azide and trimethylsilyl azide have been used as organic alternatives to the azide anion. Ammonium azide is frequently used and is generated in situ from sodium azide and ammonium chloride in DMF. The fused hetero-cycle 158 ATTz has been synthesized from the reaction of 3,6-diaminotetrazine 157 with nitrous acid and then sodium azide.103...
Other nitrating agents 1
3.2.6.1 Boron trifluoride hydrate-potassium nitrate Olah and co-workers55 reported using a nitrating agent composed of boron trifluoride hydrate and potassium nitrate for the O-nitration of alcohols. The method provides a route to nitrate esters of high purity and essentially free from nitrite esters. This reagent is also nonoxidizing. Olah found that a range of primary and secondary alcohols could be converted to their nitrate esters with this reagent 2-methyl-1-propyl nitrate 62 , n-pentyl...