Science of synthesis : Houben-Weyl methods of molecular transformations. Nitro, Nitroso, Azo, Azoxy, and Diazonium Compounds, Azides, Triazenes, and Tetrazenes

704 Pages·2009·6.771 MB·English

by  Banert K. (ed.)

VII
Volume Editor’s Preface
Thisvolume of Scienceof Synthesis is concernedwith thechemistry of nitrogenfunc-
tionalities bonded to sp3-hybridized carbon atoms of alkyl groups or, in some cases, to
sp2-hybridizedcarbonatomsofaryl,vinyl,oracylgroups.Themethodstopreparethecor-
responding compounds withsuchnitrogenfunctionalities areveryimportantandmani-
fold,andthuscannotbesummarizedinonevolumealone.Therefore,amines,ammonium
salts, haloamines, hydroxylamines, hydrazines, triazanes, and tetrazanes are covered in
Volume 40 of Science of Synthesis, whereas nitro-, nitroso-, and azidoalkanes, N-nitro-
andN-nitrosoamines,azo,azoxy,andaliphaticdiazoniumcompounds,alkyltriazenesand
-tetrazenes,andN,N-dihaloaminesarediscussed inVolume41.Severalrepresentativesof
theseproductclasseshavebeenknownformorethan100years.Inrecentyears,however,
new methods of synthesis or significant improvements to known reactions have been
reported for all product classes covered in Volume 41. Thus, this volume, like all other
volumesofScienceofSynthesis,willhelpresearchchemists inindustryandacademia
tounderstandandcreativelyapplytheextensiveknowledgeintheareaoforganicsynthesis.
Iwouldliketothankall17authorsfortheirvaluablecontributions,whichrepresent
themajorpartofthiswork.Inparticular,theirpatienceinconnectionwithmyquestions
andspecialwishesshouldbementioned.Furthermore,Iamgratefulanddeeplyimpressed
by the professional work of the competent team at the editorial office of Thieme in
Stuttgart.SuchavolumeofScienceofSynthesiscannotbeproducedwithouttheengage-
mentoftheeditorialstafftomovetheprojectahead.Iamalsothankfultomyco-workers
atChemnitzUniversityofTechnology,whosupportedmemanytimes.Finally,Iamgrate-
ful to Dr. Joe P. Richmond, who convinced me some time ago that editing this volume
would be a worthwhile undertaking. He also helped me at the planning stage of this
volume,andthushecatalyzedthefirststeps,whicharealwaysthemostcritical.
VolumeEditor
KlausBanert Chemnitz,November2009
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
IX
Volume 41:
Nitro, Nitroso, Azo, Azoxy, and Diazonium Compounds,
Azides, Triazenes, and Tetrazenes
Preface .................................................................... V
VolumeEditor’sPreface .................................................. VII
Table ofContents ......................................................... XI
Introduction
K. Banert .................................................................. 1
41.1 Product Class 1:Nitroalkanes
R.A. AitkenandK. M.Aitken .............................................. 9
41.2 Product Class 2:Nitrosoalkanes andNitroso Acetals(N,N-Dialkoxyamines)
H.-U. Reissig,B. Dugovic(cid:1),andR.Zimmer .................................. 259
41.3 ProductClass3: N-Nitroamines
U. Jahn .................................................................... 371
41.4 Product Class 4:N-Nitrosoamines
M.M. K.Boysen ........................................................... 437
41.5 Product Class 5:Aliphatic AzoxyCompounds (Aliphatic Diazene Oxides)
M.M. K.Boysen ........................................................... 449
41.6 Product Class 6:Aliphatic AzoCompounds
S.Kempa,L. Wallach,andK. Rück-Braun ................................... 459
41.7 Product Class 7:Diazonium Compounds
S.Kubik ................................................................... 507
41.8 Product Class 8:Azidoalkanes
S.Bräse,B. Lesch, andV. Zimmermann .................................... 543
41.9 Product Class 9:Alkyltriazenes
N.Jung andS.Bräse ....................................................... 613
41.10 Product Class 10: Alkyltetrazenes
N.Jung andS.Bräse ....................................................... 641
41.11 Product Class 11: N,N-Dihaloamines
S.J. Collier andW.Xiang .................................................. 651
Keyword Index ............................................................ 681
Author Index .............................................................. 721
Abbreviations ............................................................. 765
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
XI
Table of Contents
Introduction
K. Banert
Introduction ............................................................... 1
41.1 Product Class 1:Nitroalkanes
R.A. AitkenandK. M.Aitken
41.1 Product Class 1:Nitroalkanes .............................................. 9
41.1.1 Synthesisof Product Class 1 ................................................ 9
41.1.1.1 Synthesisby Substitution ................................................... 9
41.1.1.1.1 Method 1: Substitution ofHydrogen UsingNitric Acid .................. 9
41.1.1.1.1.1 Variation 1: UsingDilute Nitric Acid ..................................... 9
41.1.1.1.1.2 Variation 2: UsingConcentrated orFuming Nitric Acid ................... 10
41.1.1.1.1.3 Variation 3: UsingNitric Acid with SulfuricAcid .......................... 12
41.1.1.1.1.4 Variation 4: UsingNitric Acid with Acetic Acid ........................... 13
41.1.1.1.1.5 Variation 5: UsingNitric Acid inIonic Liquids ............................ 13
41.1.1.1.1.6 Variation 6: UsingNitric Acid intheGas Phase .......................... 13
41.1.1.1.1.7 Variation 7: UsingNitric Acid with Oxygen andHalogens
intheGas Phase ............................................ 14
41.1.1.1.2 Method 2: Substitution ofHydrogen UsingMetalNitrates .............. 15
41.1.1.1.2.1 Variation 1: UsingCopper(II) orManganese(II) Nitrates .................. 15
41.1.1.1.2.2 Variation 2: UsingAluminumTrinitrate .................................. 15
41.1.1.1.3 Method 3: Substitution ofHydrogen UsingSulfuric Acid and
AmmoniumNitrate ......................................... 15
41.1.1.1.4 Method 4: Substitution ofHydrogen UsingNitrogen Dioxide ........... 15
41.1.1.1.4.1 Variation 1: Without AdditionalReagents ................................ 15
41.1.1.1.4.2 Variation 2: WithOxygen ................................................ 16
41.1.1.1.4.3 Variation 3: WithHydrogen Peroxide .................................... 17
41.1.1.1.5 Method 5: Substitution ofHydrogen UsingSodium Nitrite and
Silver(I) Nitrate .............................................. 17
41.1.1.1.6 Method 6: Substitution ofHydrogen UsingAlkyl Nitrites ............... 17
41.1.1.1.6.1 Variation 1: Without AdditionalReagents ................................ 17
41.1.1.1.6.2 Variation 2: With3-Methylbutyl Nitrite andButyllithium ................. 18
41.1.1.1.7 Method 7: Substitution ofHydrogen Using
AlkylNitrates witha Base ................................... 18
41.1.1.1.8 Method 8: Substitution ofHydrogen Using
2,4,6-Trichloro-N-nitroaniline ................................ 20
41.1.1.1.9 Method 9: Substitution ofLithium ...................................... 20
41.1.1.1.10 Method 10: Substitution ofPotassium ................................... 20
41.1.1.1.11 Method 11: Substitution ofMagnesium .................................. 20
41.1.1.1.12 Method 12: Substitution ofMercury ..................................... 21
41.1.1.1.13 Method 13: Substitution ofa CarboxyGroup ............................ 21
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
XII TableofContents
41.1.1.1.14 Method 14: Substitution ofa CyanoGroup .............................. 22
41.1.1.1.15 Method 15: Substitution ofChlorineUsingSodium Nitrite ............... 22
41.1.1.1.15.1 Variation 1: Without AdditionalReagents ................................ 23
41.1.1.1.15.2 Variation 2: WithUrea .................................................. 23
41.1.1.1.15.3 Variation 3: WithBenzene-1,3,5-triol .................................... 24
41.1.1.1.16 Method 16: Substitution ofChlorineUsingPotassium Nitrite ............ 24
41.1.1.1.16.1 Variation 1: In thePresence ofa Base ................................... 24
41.1.1.1.16.2 Variation 2: WithCrown Ethers .......................................... 25
41.1.1.1.17 Method 17: Substitution ofChlorineUsingSilver(I) Nitrite ............... 25
41.1.1.1.17.1 Variation 1: Without AdditionalReagents ................................ 25
41.1.1.1.17.2 Variation 2: WithUrea .................................................. 26
41.1.1.1.18 Method 18: Substitution ofChlorineUsingMercury(I) Nitrite ............ 27
41.1.1.1.19 Method 19: Substitution ofChlorineUsing
Polymer-Supported Nitrite .................................. 27
41.1.1.1.20 Method 20: Substitution ofBromineUsingSodium Nitrite ............... 27
41.1.1.1.20.1 Variation 1: Without AdditionalReagents ................................ 27
41.1.1.1.20.2 Variation 2: WithBenzene-1,2-diol ...................................... 29
41.1.1.1.20.3 Variation 3: WithBenzene-1,3,5-triol .................................... 29
41.1.1.1.20.4 Variation 4: WithUrea .................................................. 31
41.1.1.1.20.5 Variation 5: WithUrea andBenzene-1,3,5-triol .......................... 32
41.1.1.1.20.6 Variation 6: Witha Phase-Transfer Catalyst .............................. 34
41.1.1.1.20.7 Variation 7: WithanIonic Liquid ......................................... 34
41.1.1.1.21 Method 21: Substitution ofBromineUsingPotassium Nitrite ............ 34
41.1.1.1.22 Method 22: Substitution ofBromineUsingSilver(I) Nitrite ............... 35
41.1.1.1.23 Method 23: Substitution ofBromineUsingAmmonium Nitrites .......... 38
41.1.1.1.24 Method 24: Substitution ofBromineUsingPolymer-Supported Nitrite ... 39
41.1.1.1.25 Method 25: Substitution ofIodine UsingSodium Nitrite ................. 39
41.1.1.1.25.1 Variation 1: Without AdditionalReagents ................................ 40
41.1.1.1.25.2 Variation 2: WithBenzene-1,3,5-triol .................................... 41
41.1.1.1.25.3 Variation 3: WithUrea .................................................. 41
41.1.1.1.25.4 Variation 4: WithUrea andBenzene-1,3,5-triol .......................... 42
41.1.1.1.26 Method 26: Substitution ofIodine UsingSilver(I)Nitrite ................. 43
41.1.1.1.27 Method 27: Substitution ofIodine UsingAmmoniumNitrites ............ 46
41.1.1.1.28 Method 28: Substitution ofIodine UsingPolymer-Supported Nitrite ...... 46
41.1.1.1.29 Method 29: Substitution ofSulfates ..................................... 46
41.1.1.1.30 Method 30: Substitution ofSulfonates ................................... 47
41.1.1.1.31 Method 31: Substitution ofOxoniumTetrafluoroborates ................. 48
41.1.1.1.32 Method 32: Substitution ofNitrogen inAzoCompounds ................ 48
41.1.1.2 Synthesisby Oxidation Reactions ........................................... 49
41.1.1.2.1 Method 1: Oxidation ofa Primary AminoGroupUsingCaro’s Acid ..... 49
41.1.1.2.2 Method 2: Oxidation ofa Primary AminoGroupUsing
Hypofluorous Acid .......................................... 49
41.1.1.2.3 Method 3: Oxidation ofa Primary AminoGroupUsing
Organic Peroxides ........................................... 50
41.1.1.2.3.1 Variation 1: UsingDimethyldioxirane .................................... 50
41.1.1.2.3.2 Variation 2: Using tert-ButylHydroperoxide andChromium Silicalite ..... 52
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
TableofContents XIII
41.1.1.2.3.3 Variation 3: Using tert-ButylHydroperoxide andZirconium(IV)
tert-Butoxide ................................................ 52
41.1.1.2.3.4 Variation 4: UsingOxaziridinium Salts ................................... 53
41.1.1.2.4 Method 4: Oxidation ofa Primary AminoGroupUsing
Organic PeroxyAcids ....................................... 53
41.1.1.2.4.1 Variation 1: UsingPeracetic Acid ........................................ 53
41.1.1.2.4.2 Variation 2: Using3-Chloroperoxybenzoic Acid .......................... 54
41.1.1.2.5 Method 5: Oxidation ofa Primary AminoGroupUsingOzone .......... 55
41.1.1.2.6 Method 6: Oxidation ofanAzido GroupUsingHypofluorous Acid ...... 56
41.1.1.2.7 Method 7: Oxidation ofanAzido GroupUsingOzone
anda Phosphine ............................................ 57
41.1.1.2.8 Method 8: Oxidation ofa Hydroxyamino Group UsingNitric Acid ....... 57
41.1.1.2.8.1 Variation 1: Without AdditionalReagents ................................ 57
41.1.1.2.8.2 Variation 2: WithAmmonium Nitrate .................................... 58
41.1.1.2.9 Method 9: Oxidation ofa Hydroxyamino Group Using
Potassium PermanganateinSulfuric Acid ................... 58
41.1.1.2.10 Method 10: Oxidation ofa Nitroso GroupUsing Nitric Acid .............. 59
41.1.1.2.10.1 Variation 1: WithAmmonium Nitrate .................................... 59
41.1.1.2.10.2 Variation 2: WithAcetic Acid ............................................ 59
41.1.1.2.11 Method 11: Oxidation ofa Nitroso GroupUsing Hydrogen Peroxide ..... 59
41.1.1.2.11.1 Variation 1: Without AdditionalReagents ................................ 59
41.1.1.2.11.2 Variation 2: WithSulfuric Acid ........................................... 59
41.1.1.2.12 Method 12: Oxidation ofa Nitroso GroupUsing Manganese(VII) ......... 60
41.1.1.2.12.1 Variation 1: UsingPotassium PermanganateinAcetone ................. 60
41.1.1.2.12.2 Variation 2: UsingManganese(VII) Oxide ................................ 60
41.1.1.2.13 Method 13: Oxidation ofa Nitroso GroupUsing Chromium(VI) .......... 60
41.1.1.2.13.1 Variation 1: UsingChromium(VI) Oxide Alone ........................... 60
41.1.1.2.13.2 Variation 2: UsingChromium(VI) Oxide andAcetic Acid ................. 60
41.1.1.2.13.3 Variation 3: UsingChromium(VI) Oxide withAcetic
andSulfuric Acids ........................................... 61
41.1.1.2.14 Method 14: Oxidation ofa Nitroso GroupUsing Lead(IV) Oxide .......... 62
41.1.1.2.15 Method 15: Oxidation ofa Nitroso GroupUsing Oxidizing Gases ......... 62
41.1.1.2.15.1 Variation 1: UsingAir .................................................... 62
41.1.1.2.15.2 Variation 2: UsingOxygen ............................................... 62
41.1.1.2.15.3 Variation 3: UsingNitrogen Dioxide/Dinitrogen Tetroxide ................ 62
41.1.1.2.16 Method 16: Oxidation ofa Nitroso GroupUsing OrganicPeroxy Acids ... 63
41.1.1.2.16.1 Variation 1: UsingTrifluoroperoxyacetic Acid ............................ 63
41.1.1.2.16.2 Variation 2: Using3-Chloroperoxybenzoic Acid .......................... 63
41.1.1.2.17 Method 17: Photochemical Oxidation ofa Nitroso Group ................ 64
41.1.1.2.18 Method 18: Oxidation ofa Nitroso GroupUsing Iodosylbenzene ......... 64
41.1.1.2.19 Method 19: Oxidation ofanOximeGroup UsingNitric Acid ............. 64
41.1.1.2.19.1 Variation 1: Without Other Reagents .................................... 64
41.1.1.2.19.2 Variation 2: WithSulfuric Acid ........................................... 64
41.1.1.2.20 Method 20: Oxidation ofanOximeGroup UsingPeroxysulfates .......... 65
41.1.1.2.20.1 Variation 1: UsingCaro’s Acid ........................................... 65
41.1.1.2.20.2 Variation 2: UsingOxone ................................................ 65
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
XIV TableofContents
41.1.1.2.21 Method 21: Oxidation ofanOximeGroup UsingHydrogen Peroxide with
Urea andMethyltrioxorhenium(VII) Catalyst ................. 66
41.1.1.2.22 Method 22: Oxidation ofanOximeGroup UsingLead(IV) Acetate ....... 66
41.1.1.2.23 Method 23: Oxidation ofanOximeGroup with
Potassium Permanganate ................................... 66
41.1.1.2.24 Method 24: Oxidation ofanOximeGroup withSodium Perborate ....... 67
41.1.1.2.25 Method 25: Oxidation ofanOximeGroup Using
Organic PeroxyAcids ....................................... 67
41.1.1.2.25.1 Variation 1: UsingTrifluoroperoxyacetic Acid ............................ 67
41.1.1.2.25.2 Variation 2: Using3-Chloroperoxybenzoic Acid .......................... 70
41.1.1.2.26 Method 26: Oxidation ofanOximeGroup Using
Dinitrogen Tetroxide ........................................ 71
41.1.1.2.27 Method 27: Enzymatic Oxidation ofanOximeGroup .................... 71
41.1.1.3 Synthesisby AdditionReactions ............................................. 71
41.1.1.3.1 Method 1: Oxidative Nitrosation ofanOximeGroup ................... 72
41.1.1.3.2 Method 2: Oxidative Nitration ofanOximeUsing Nitric Acid ........... 72
41.1.1.3.2.1 Variation 1: Without AdditionalReagents ................................ 72
41.1.1.3.2.2 Variation 2: Followed byHydrogen Peroxide ............................. 73
41.1.1.3.2.3 Variation 3: WithAcetic Acid,Followed by Hydrogen Peroxide ........... 73
41.1.1.3.3 Method 3: Oxidative Nitration ofanOximeUsing NitrogenOxides ..... 74
41.1.1.3.3.1 Variation 1: UsingNitrogen Dioxide/Dinitrogen Tetroxide ................ 74
41.1.1.3.3.2 Variation 2: UsingNitrogen Dioxide andMagnesium Sulfate ............. 74
41.1.1.3.3.3 Variation 3: UsingDinitrogen Pentoxide ................................. 75
41.1.1.3.4 Method 4: Oxidative Chlorination ofanOximeUsingChlorine .......... 76
41.1.1.3.4.1 Variation 1: UsingChlorineFollowed by Ozone .......................... 76
41.1.1.3.4.2 Variation 2: UsingChlorinewith Hydrochloric, Nitric,
andAcetic Acids ............................................ 77
41.1.1.3.5 Method 5: Oxidative Chlorination ofanOxime
UsingSodium Hypochlorite ................................. 77
41.1.1.3.6 Method 6: Oxidative Chlorination ofanOxime
UsingSodium Chloride,Oxone, andAlumina ................ 77
41.1.1.3.7 Method 7: Oxidative Chlorination ofanOxime
UsingHydrochloric Acid andHydrogen Peroxide ............ 78
41.1.1.3.8 Method 8: Oxidative Bromination ofanOxime
UsingSodium Hypobromite Followedby Nitric Acid ......... 78
41.1.1.3.9 Method 9: Oxidative Bromination ofanOxime
UsingN-Bromoacetamide ................................... 79
41.1.1.3.10 Method 10: Oxidative Bromination ofanOxime
UsingN-Bromosuccinimide andPotassium Carbonate ....... 80
41.1.1.3.11 Method 11: Oxidative Bromination ofanOxime
UsingSodium Bromide,Oxone, andAlumina ................ 81
41.1.1.3.12 Method 12: Oxidative Acetoxylation ofanOximeUsingLead(IV)
Acetate, Hydrogen Peroxide,andSodium Nitrite ............ 81
41.1.1.3.13 Method 13: Additionof NitrousAcid toanAlkene ....................... 82
41.1.1.3.13.1 Variation 1: UsingSodium Nitrite andAcetic Acid ....................... 82
41.1.1.3.13.2 Variation 2: UsingSodium Nitrite andHydrochloric Acid ................. 82
41.1.1.3.14 Method 14: Additionof Tetranitromethane toanAlkene ................ 83
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
TableofContents XV
41.1.1.3.15 Method 15: Nitrofluorination ofanAlkene ............................... 84
41.1.1.3.15.1 Variation 1: UsingNitric andHydrofluoric Acids ......................... 84
41.1.1.3.15.2 Variation 2: UsingNitryl Fluoride ........................................ 85
41.1.1.3.15.3 Variation 3: UsingNitronium Tetrafluoroborate
andPyridiniumFluoride ..................................... 85
41.1.1.3.16 Method 16: Nitrochlorination ofanAlkene .............................. 86
41.1.1.3.16.1 Variation 1: UsingNitrosyl Chloride ...................................... 86
41.1.1.3.16.2 Variation 2: UsingNitrosyl Chloride,Nitrogen Dioxide,
andOxygen ................................................. 87
41.1.1.3.16.3 Variation 3: UsingNitryl Chloride ........................................ 88
41.1.1.3.16.4 Variation 4: UsingNitrogen Dioxide andBoronTrifluoride ............... 89
41.1.1.3.16.5 Variation 5: UsingNitrogen Dioxide andChlorine ........................ 89
41.1.1.3.16.6 Variation 6: UsingNitrogen Dioxide,Phosphorus Trichloride,
andOxygen ................................................. 90
41.1.1.3.17 Method 17: Nitrobromination ofanAlkene .............................. 90
41.1.1.3.17.1 Variation 1: UsingSodium Nitrite, Mercury(II) Chloride,andBromine .... 90
41.1.1.3.17.2 Variation 2: UsingNitrosyl Bromide ...................................... 91
41.1.1.3.17.3 Variation 3: UsingNitrogen Dioxide andBromine ........................ 92
41.1.1.3.17.4 Variation 4: UsingNitrogen Dioxide,Phosphorus Tribromide,
andOxygen ................................................. 92
41.1.1.3.18 Method 18: Nitroiodination ofanAlkene ................................ 92
41.1.1.3.18.1 Variation 1: UsingSilver(I) Nitrite andIodine ............................ 92
41.1.1.3.18.2 Variation 2: UsingNitrogen Dioxide andIodine .......................... 93
41.1.1.3.19 Method 19: Nitroacetamidation ofanAlkene ............................ 94
41.1.1.3.20 Method 20: Nitronitrosation ofanAlkene (Synthesis ofc-Nitrosites) ..... 94
41.1.1.3.20.1 Variation 1: UsingSodium Nitrite andSulfuric Acid ...................... 95
41.1.1.3.20.2 Variation 2: UsingSodium Nitrite andHydrochloric Acid ................. 96
41.1.1.3.20.3 Variation 3: UsingSodium Nitrite andAcetic Acid ....................... 96
41.1.1.3.20.4 Variation 4: UsingSodium Nitrite andPhosphoric Acid .................. 97
41.1.1.3.20.5 Variation 5: UsingNitric Oxide with Catalysts ............................ 97
41.1.1.3.20.6 Variation 6: UsingNitric Oxide with Air .................................. 98
41.1.1.3.21 Method 21: 1,2-Dinitration of anAlkene ................................. 99
41.1.1.3.21.1 Variation 1: UsingPentyl Nitrite andAcetic Acid ......................... 99
41.1.1.3.21.2 Variation 2: UsingNitrogen Dioxide ..................................... 99
41.1.1.3.21.3 Variation 3: UsingNitrogen Dioxide andOxygen ......................... 101
41.1.1.3.22 Method 22: Nitrohydroxylation ofanAlkene ............................. 101
41.1.1.3.22.1 Variation 1: UsingNitric Acid ............................................ 101
41.1.1.3.22.2 Variation 2: UsingNitric andSulfuric Acids .............................. 102
41.1.1.3.22.3 Variation 3: UsingSodium Nitrite andAmmonium
Cerium(IV) Nitrate .......................................... 102
41.1.1.3.22.4 Variation 4: UsingDinitrogen Trioxide ................................... 103
41.1.1.3.22.5 Variation 5: UsingNitrogen Dioxide ..................................... 103
41.1.1.3.22.6 Variation 6: UsingOrganic Nitrating Agents ............................. 104
41.1.1.3.23 Method 23: Nitromethoxylation ofanAlkene Using
Tetranitromethane andMethanol ........................... 105
41.1.1.3.24 Method 24: Additionof aNitro Groupanda NitrateGroup
toanAlkene ................................................ 105
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG
XVI TableofContents
41.1.1.3.24.1 Variation 1: UsingNitric Acid ............................................ 105
41.1.1.3.24.2 Variation 2: UsingNitrogen Dioxide andOxygen ......................... 105
41.1.1.3.24.3 Variation 3: UsingDinitrogen Pentoxide ................................. 106
41.1.1.3.25 Method 25: Nitroacetoxylation ofan Alkene ............................. 108
41.1.1.3.25.1 Variation 1: UsingAcetyl Nitrate ......................................... 108
41.1.1.3.25.2 Variation 2: UsingNitric andSulfuric Acids Followed
byAcetic Anhydride ......................................... 109
41.1.1.3.26 Method 26: Additionof aNitro Groupanda Perchlorate Group
toanAlkene ................................................ 109
41.1.1.3.27 Method 27: Additionof aNitro GroupandanEthylSulfate Group
toanAlkene ................................................ 110
41.1.1.3.28 Method 28: Conversion ofAlkenes intoa-Nitro Ketones ................. 110
41.1.1.3.28.1 Variation 1: UsingNitrogen Dioxide andOxygen
inDimethyl Sulfoxide ....................................... 110
41.1.1.3.28.2 Variation 2: UsingChlorotrimethylsilane, Silver(I)Nitrate,
andChromium(VI) Oxide .................................... 111
41.1.1.3.28.3 Variation 3: UsingChlorotrimethylsilane, Silver(I)Nitrate,
andDimethyl Sulfoxide ..................................... 112
41.1.1.3.29 Method 29: Nitration ofSilyl Enol Ethers ................................ 112
41.1.1.3.29.1 Variation 1: UsingTetranitromethane .................................... 112
41.1.1.3.29.2 Variation 2: UsingNitronium Ethyl Sulfate ............................... 113
41.1.1.3.30 Method 30: Destructive Nitration ........................................ 113
41.1.1.4 Synthesisby Rearrangement orDisproportionation .......................... 115
41.1.1.4.1 Method 1: Rearrangement ofAlkylNitrates ............................ 115
41.1.1.4.2 Method 2: Disproportionation Reactions ................................ 116
41.1.1.5 Synthesiswith Retention oftheNitroGroup ................................ 116
41.1.1.5.1 Method 1: AlkylationofNitroalkanes with AlkylHalides ................ 117
41.1.1.5.1.1 Variation 1: WithFluoroalkanes .......................................... 117
41.1.1.5.1.2 Variation 2: WithChloroalkanes ......................................... 117
41.1.1.5.1.3 Variation 3: WithBromoalkanes ......................................... 119
41.1.1.5.1.4 Variation 4: WithIodoalkanes ........................................... 121
41.1.1.5.2 Method 2: AlkylationofNitroalkanes with Alkylammonium Salts ....... 122
41.1.1.5.3 Method 3: AlkylationofNitroalkanes with Alkyl(phenyl)iodonium
Reagents ................................................... 122
41.1.1.5.4 Method 4: AlkylationofNitroalkanes with AlkylArenesulfonates ........ 123
41.1.1.5.5 Method 5: AlkylationofNitroalkanes with AlkylAryl Sulfones ........... 124
41.1.1.5.6 Method 6: AlkylationofNitroalkanes with Hydratesor
Hemiacetals ofAldehydes ................................... 125
41.1.1.5.7 Method 7: AlkylationofNitroalkanes with AlkylAzides ................. 126
41.1.1.5.8 Method 8: AlkylationofNitroalkanes with anAlkylDifluoromethyl
Nitrite ...................................................... 126
41.1.1.5.9 Method 9: Vinylation ofNitroalkanes ................................... 126
41.1.1.5.10 Method 10: Arylation ofNitroalkanes .................................... 127
41.1.1.5.11 Method 11: Allylation ofNitroalkanes .................................... 129
41.1.1.5.11.1 Variation 1: Nucleophilic Substitution .................................... 129
41.1.1.5.11.2 Variation 2: Palladium-Catalyzed Allylation ............................... 131
Science of Synthesis Original Edition Volume 41
© Georg Thieme Verlag KG