Compilation of Nitroethane SynthesesAll Methods #1-23 have basic abstracts, links and information to be found in the thread beginning with this post:
Post 103078
(rev drone: "What can be done to improve the performance of clandestine nitroethane synth?", Chemistry Discourse)
OR AT:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitroethane.html
Additional information links and posts will be listed underneath its respective synthesis as they become available. Some safety information regarding Nitroethane:Nitroethane, Ethyl nitrate and Ethyl NitritePost 392844
(Rhodium: "Nitroethane from ethanol", Chemistry Discourse)Method 1: from sodium ethyl sulfate and a metal nitritepatent CH74333
Text for patent above:Post 436963
(Organikum: "Patents on nitroethane - translation", Chemistry Discourse) Method 2: from diethyl sulfate and sodium nitritepatent CH75523
Text for patent above:Post 437812
(jimwig: "No 436362 nitroethane revisited again too...", Chemistry Discourse)Experiences with this method:Post 384841
(roger2003: "Method 2: from diethyl sulfate and sodium nitrite ...", Chemistry Discourse)Prep’ing dialkylsulfates:Experiences with preparations:Post 233762 (missing)
(Antoncho: "Kitchen nitroalkane success!", Chemistry Discourse)Post 251119
(Bandil: "Nitroethane ala Antoncho succes", Novel Discourse)Post 399668
(Antoncho: "Some problems with nitroethane synth...", Methods Discourse)Method 3: from ethyl bromide (iodide) and sodium nitrite (dmf)Method 4 : from ethyl halide and silver nitriteMethod 5: oxidation of ethyl amine with peracids (m-perbenzoicacid)See Method 21:Method 6: oxidation of ethyl amine with potassium permanganateSee Method 21:http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0845
Method 7: destructive distillation of alpha-bromopropionic acid with sodium nitriteSynthesis of alpha-bromopropionic acidhttp://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1p0115
Method 8: oxidation of ethyl amine to nitroethane with dimethyldioxiraneMethod 9: isomerization of ethyl nitrite to nitroethane over asbestos catalystMethod 10: ethyl bromide, DMSO, NaNO2 and phloroglucinol dihydratePreparation of PhloroglucinolPost 385985
(lugh: "Phlorglucinol synthesis details", Chemistry Discourse)Post 331397
(hypo: "Phloroglucinol and pyrocatechol from phenol", Novel Discourse)Post 199920
(obituary: "synth of phloroglucinol", Methods Discourse)Other nitrite scavenging possibilities:Post 276855
(starlight: "phloroglucinol / catechol / pyrogallol", Chemistry Discourse)Method 11: 3-chloropropionic acid sodium salt, and NaNO2Originally found by WizardX, but Joyman posted the method detailsPost 238127
(joyman: "Re: What can be done to improve the performance of clandestine nitroethane synth?", Chemistry Discourse)The orginal article on which this method is based:http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0401
Another modification of the method above:Post 236612
(malvaxman: "Nice nitroethane synth by WizardX", Methods Discourse)Method 12: most complicated synthMethod 13: electrochemical oxidation ---- not possible by method below Method 14, 15 and 16: Vapor Phase nitration of propane, ethane and ethanol respectivelyOther vapor-phase nitration references:Post 396687
(Aurelius: "Other Patents", Chemistry Discourse)Post 398745
(Aurelius: "Some Reference Materials in the Compilation", Chemistry Discourse)Patent US4431842
Text of the patent above:Post 396685
(Aurelius: "Patent References US patent", Chemistry Discourse)Method 17: Distillation of alpha-bromopropionic acids with NaNO2 in the presence of Magnesium Sulfate in DMSOPatent US4319059
Text for this patent may be found here:
Post 396684
(Aurelius: "Patent References US patent 4319059", Chemistry Discourse)Patent US4431842
Text of the patent above:Post 396685
(Aurelius: "Patent References US patent", Chemistry Discourse)Method 18: Oxidation of alanine with permanganate followed by decarboxylationMethod 19: Reduction of acetaldehyde oxime and oxidation of the productMethod 20: reduction of nitroethene to nitroethane using 2-phenylbenzimidazolineMethod 21: Oxidation of ethyl amineNitroethane via Permanganate (Buffered with MgSO4 and not) oxidation of ethyl amine:http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0845
The above is just like Method 6Oxidation via H2O2:Oxidation with Peracids acid (Buffered and not):The above is just like Method 5Oxidation with THBP over CrS-2:Oxidation with DMDO:Each of the oxidations just listed can be found at this link:Post 398745
(Aurelius: "Some Reference Materials in the Compilation", Chemistry Discourse)Synthesis of Ethyl Amine:Ethyl amine from acetonitrile via Al/Hg:Post 2813 (missing)
(BrightStar: "Re: nitroethene", Chemistry Discourse)Method 22: Nitroethane from propyl nitrateJ.B. Levy ; F.J. Adrian, J. Amer. Soc. 77, 2015 (1954)Method 23: Nitroethane from nitroethene (and nitroethanol) Nitroethane via nitroethene reduction with NaBH4:Post 216376 (missing)
(slappy: "Re: Nitroethene Reduction to Nitroethane", Chemistry Discourse)Nitroethane via nitroethene reduction with Baker’s Yeast:Post 108516
(dormouse: "A new reducing agent for nitrostyrenes: bakers yeast! -Labrat", Novel Discourse)Synthesis of Nitroethene:Nitromethane, formaldehyde and ammonium acetatenot certain that nitroethanol isn’t formed insteadPost 2716 (missing)
(psyloxy: "nitroethene", Chemistry Discourse)Vapor-phase Nitromethane, formaldehyde over catalystPost 216189 (missing)
(halfapint: "Nitroethene Reduction to Nitroethane", Chemistry Discourse)Dehydration of Nitroethanolno method given, should be performed with H2SO4, H3PO4 or KHSO4 Synthesis of Nitroethanol:Nitromethane, formaldehyde in alkaline aqueous solution:Post 216189 (missing)
(halfapint: "Nitroethene Reduction to Nitroethane", Chemistry Discourse)Method 24: Nitroethane from ethanol (doesn’t work as proposed in article 1)Proposed method:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/alcohol2nitro.html
Reality:
https://www.thevespiary.org/rhodium/Rhodium/pdf/nitroalcohol.pdf
The first article shows the formation of nitroethane. However, the second article presents convincing evidence that ethyl nitrite is actually formed. Method 9 gives an option for ethyl nitrite to nitroethane- however, it is considered an industrial procedure.Method 25: Oxidation of acetaldoxime to nitroethane with Na perboratePost 435910 (missing)
(Lego: "Oximes to nitro alkanes with sodium perborate", Chemistry Discourse)Method 26: Oxidation of acetaldoxime with Oxone in MeCNPost 435890 (missing)
(Lego: "Oxidation of oximes to nitroalkanes", Chemistry Discourse)Method 27: Oxidation of acetaldoxime with peroxytrifluoroacetic acid J. Am. Chem. Soc., 1955, 77, 4557Method 28: Oxidation of acetaldoxime with Urea-H2O2 complex in MeCN Tet. Lett, 1992, 33, 4835Method 29: Oxidation of acetaldoxime with Benz-Mo in MeCN Synlett, 1996, 1093Method 30: Direct Nitration of Ethane (alkanes) with Nitronium HexafluorophosphatePost 471835
(pHarmacist: "Direct Nitration of Alkanes", Chemistry Discourse)Method 31: Ethyl Halide to Nitroethane w/PTCPost 474349
(Lego: "Nitroalkanes from bromoalkanes with PTC", Chemistry Discourse)References for various methods given above:Post 474663
(Rhodium: "original nitroethane literature", Methods Discourse)