ORGANIC CHEMISTRY OF EXPLOSIVES
CONTENTS 1 SYNTHETIC ROUTES TO ALIPHATIC C-NITRO FUNCTIONALITY 11 INTRODUCTION 12 ALIPHATIC C-NITRO COMPOUNDS AS EXPLOSIVES 13 DIRECT NITRATION OF ALKANES 14 ADDITION OF NITRIC ACID, NITROGEN OXIDES AND RELATED COMPOUNDS TO UNSATURATED BONDS 141 NITRIC ACID AND ITS MIXTURES 142 NITROGEN DIOXIDE 143 DINITROGEN PENTOXIDE 144 NITROUS OXIDE AND DINITROGEN TRIOXIDE 145 OTHER NITRATING AGENTS 15 HALIDE DISPLACEMENT 151 VICTOR MEYER REACTION 152 MODI?ED VICTOR MEYER REACTION 153 TER MEER REACTION 154 DISPLACEMENTS USING NITRONATE SALTS AS NUCLEOPHILES 16 OXIDATION AND NITRATION OF C–N BONDS 161 OXIDATION AND NITRATION OF OXIMES 162 OXIDATION OF AMINES 163 NITRATION OF NITRONATE SALTS 164 OXIDATION OF PSEUDONITROLES 165 OXIDATION OF ISOCYANATES 166 OXIDATION OF NITROSOALKANES 17 KAPLAN–SHECHTER REACTION 18 NITRATION OF COMPOUNDS CONTAINING ACIDIC HYDROGEN 181 ALKALINE NITRATION 182 ACIDIC NITRATION 19 OXIDATIVE DIMERIZATION 110 ADDITION AND CONDENSATION REACTIONS 1101 1,2-ADDITION REACTIONS 1102 1,4-ADDITION REACTIONS 1103 MANNICH REACTION 1104 HENRY REACTION 111 DERIVATIVES OF POLYNITROALIPHATIC ALCOHOLS 112 MISCELLANEOUS 1121 1,1-DIAMINO-2,2-DINITROETHYLENES 1122 OTHER ROUTES TO ALIPHATIC NITRO COMPOUNDS 1123 SELECTIVE REDUCTIONS 113 CHEMICAL STABILITY OF POLYNITROALIPHATIC COMPOUNDS 1131 REACTIONS WITH MINERAL ACIDS 1132 REACTIONS WITH BASE AND NUCLEOPHILES REFERENCES 2 ENERGETIC COMPOUNDS 1: POLYNITROPOLYCYCLOALKANES 21 CAGED STRUCTURES AS ENERGETIC MATERIALS 22 CYCLOPROPANES AND SPIROCYCLOPROPANES 23 CYCLOBUTANES AND THEIR DERIVATIVES 24 CUBANES 25 HOMOCUBANES 26 PRISMANES 27 ADAMANTANES 28 POLYNITROBICYCLOALKANES 281 NORBORNANES 282 BICYCLO[330]OCTANE 283 BICYCLO[331]NONANE 3 SYNTHETIC ROUTES TO NITRATE ESTERS 31 NITRATE ESTERS AS EXPLOSIVES 32 NITRATION OF THE PARENT ALCOHOL 321 O-NITRATION WITH NITRIC ACID AND ITS MIXTURES 322 O-NITRATION WITH DINITROGEN TETROXIDE 323 O-NITRATION WITH DINITROGEN PENTOXIDE 324 O-NITRATION WITH NITRONIUM SALTS 325 TRANSFER NITRATION 326 OTHER O-NITRATING AGENTS 33 NUCLEOPHILIC DISPLACEMENT WITH NITRATE ANION 331 METATHESIS BETWEEN ALKYL HALIDES AND SILVER NITRATE 332 DECOMPOSITION OF NITRATOCARBONATES 333 DISPLACEMENT OF SULFONATE ESTERS WITH NITRATE ANION 334 DISPLACEMENT WITH MERCURY (I) NITRATE 34 NITRATE ESTERS FROM THE RING-OPENING OF STRAINED OXYGEN HETEROCYCLES 341 RING-OPENING NITRATION OF EPOXIDES 342 1,3-DINITRATE ESTERS FROM THE RING-OPENING NITRATION OF OXETANES WITH DINITROGEN PENTOXIDE 343 OTHER OXYGEN HETEROCYCLES 35 NITRODESILYLATION 36 ADDITIONS TO ALKENES 361 NITRIC ACID AND ITS MIXTURES 362 NITROGEN OXIDES 363 METAL SALTS 364 HALONITROXYLATION 37 DEAMINATION 38 MISCELLANEOUS METHODS 39 SYNTHETIC ROUTES TO SOME POLYOLS AND THEIR NITRATE ESTER DERIVATIVES 310 ENERGETIC NITRATE ESTERS 4 SYNTHETIC ROUTES TO AROMATIC C-NITRO COMPOUNDS 41 INTRODUCTION 42 POLYNITROARYLENES AS EXPLOSIVES 43 NITRATION 431 NITRATION WITH MIXED ACID 432 SUBSTRATE DERIVED REACTIVITY 433 EFFECT OF NITRATING AGENT AND REACTION CONDITIONS ON PRODUCT SELECTIVITY 434 OTHER NITRATING AGENTS 435 SIDE-REACTIONS AND BY-PRODUCTS FROM NITRATION 44 NITROSATION–OXIDATION 45 NITRAMINE REARRANGEMENT 46 REACTION OF DIAZONIUM SALTS WITH NITRITE ANION 47 OXIDATION OF ARYLAMINES, ARYLHYDROXYLAMINES AND OTHER DERIVATIVES 471 OXIDATION OF ARYLAMINES AND THEIR DERIVATIVES 472 OXIDATION OF ARYLHYDROXYLAMINES AND THEIR DERIVATIVES 48 NUCLEOPHILIC AROMATIC SUBSTITUTION 481 DISPLACEMENT OF HALIDE 482 NITRO GROUP DISPLACEMENT AND THE REACTIVITY OF POLYNITROARYLENES 483 DISPLACEMENT OF OTHER GROUPS 484 SYNTHESIS OF 1,3,5-TRIAMINO-2,4,6-TRINITROBENZENE (TATB) 49 THE CHEMISTRY OF 2,4,6-TRINITROTOLUENE (TNT) 410 CONJUGATION AND THERMALLY INSENSITIVE EXPLOSIVES 5 SYNTHETIC ROUTES TO N-NITRO FUNCTIONALITY 51 INTRODUCTION 52 NITRAMINES, NITRAMIDES AND NITRIMINES AS EXPLOSIVES 53 DIRECT NITRATION OF AMINES 531 NITRATION UNDER ACIDIC CONDITIONS 532 NITRATION WITH NONACIDIC REAGENTS 54 NITRATION OF CHLORAMINES 541 NITRATION OF DIALKYLCHLORAMINES 542 NITRATION OF ALKYLDICHLORAMINES 55 N-NITRATION OF AMIDES AND RELATED COMPOUNDS 551 NITRATION WITH ACIDIC REAGENTS 552 NITRATION WITH NONACIDIC REAGENTS 56 NITROLYSIS 561 NITROLYSIS OF AMIDES AND THEIR DERIVATIVES 562 NITROLYSIS OF N-ALKYL BONDS 563 NITROLYSIS OF NITROSAMINES 57 NITRATIVE CLEAVAGE OF OTHER NITROGEN BONDS 58 RING-OPENING NITRATION OF STRAINED NITROGEN HETEROCYCLES 581 AZIRIDINES 582 AZETIDINES 59 NITROSAMINE OXIDATION 510 HYDROLYSIS OF NITRAMIDES AND NITROUREAS 511 DEHYDRATION OF NITRATE SALTS 512 OTHER METHODS 513 PRIMARY NITRAMINES AS NUCLEOPHILES 5131 1,4-MICHAEL ADDITION REACTIONS 5132 MANNICH CONDENSATION REACTIONS 5133 CONDENSATIONS WITH FORMALDEHYDE 5134 NUCLEOPHILIC DISPLACEMENT REACTIONS 514 AROMATIC NITRAMINES 515 THE NITROLYSIS OF HEXAMINE 5151 THE SYNTHESIS OF RDX 5152 THE SYNTHESIS OF HMX 5153 EFFECT OF REACTION CONDITIONS ON THE NITROLYSIS OF HEXAMINE 5154 OTHER NITRAMINE PRODUCTS FROM THE NITROLYSIS OF HEXAMINE 6 ENERGETIC COMPOUNDS 2: NITRAMINES AND THEIR DERIVATIVES 61 CYCLOPROPANES 62 CYCLOBUTANES 63 AZETIDINES – 1,3,3-TRINITROAZETIDINE (TNAZ) 64 CUBANE–BASED NITRAMINES 65 DIAZOCINES 66 BICYCLES 67 CAGED HETEROCYCLES – ISOWURTZITANES 68 HETEROCYCLIC NITRAMINES DERIVED FROM MANNICH REACTIONS 69 NITROUREAS 610 OTHER ENERGETIC NITRAMINES 611 ENERGETIC GROUPS 6111 DINITRAMIDE ANION 6112 ALKYL N,N-DINITRAMINES 6113 N-NITROIMIDES 7 ENERGETIC COMPOUNDS 3: N-HETEROCYCLES 71 INTRODUCTION 72 5-MEMBERED RINGS – 1N – PYRROLES 73 5-MEMBERED RINGS – 2N 731 PYRAZOLES 732 IMIDAZOLES 733 1,3,4-OXADIAZOLES 734 1,2,5-OXADIAZOLES (FURAZANS) 735 BENZOFURAZANS 736 FUROXANS 737 BENZOFUROXANS 74 5-MEMBERED RINGS – 3N 741 TRIAZOLES 742 TRIAZOLONES 743 BENZOTRIAZOLES 75 5-MEMBERED RINGS – 4N 76 6-MEMBERED RINGS – 1N – PYRIDINES 77 6-MEMBERED RINGS – 2N 78 6-MEMBERED RINGS – 3N 79 6-MEMBERED RINGS – 4N 710 DIBENZOTETRAAZAPENTALENES 8 MISCELLANEOUS EXPLOSIVE COMPOUNDS 81 ORGANIC AZIDES 811 ALKYL AZIDES 812 AROMATIC AZIDES 82 PEROXIDES 83 DIAZOPHENOLS 831 DIAZOPHENOLS FROM THE DIAZOTIZATION OF AMINOPHENOLS 832 DIAZOPHENOLS FROM THE REARRANGEMENT OF O-NITROARYLNITRAMINES 84 NITROGEN-RICH COMPOUNDS FROM GUANIDINE AND ITS DERIVATIVES 9 DINITROGEN PENTOXIDE – AN ECO-FRIENDLY NITRATING AGENT 91 INTRODUCTION 92 NITRATIONS WITH DINITROGEN PENTOXIDE 93 THE CHEMISTRY OF DINITROGEN PENTOXIDE 94 PREPARATION OF DINITROGEN PENTOXIDE 95 C-NITRATION 96 N-NITRATION 97 NITROLYSIS 98 O-NITRATION 99 RING CLEAVAGE NITRATION