Compilation of Nitroethane Syntheses

[Aurelius]

Compilation of Nitroethane Syntheses

All 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 Nitrite

Post 392844

(Rhodium: "Nitroethane from ethanol", Chemistry Discourse)

Method 1: from sodium ethyl sulfate and a metal nitrite
patent CH74333
Text for patent above:

Post 436963

(Organikum: "Patents on nitroethane - translation", Chemistry Discourse)


Method 2: from diethyl sulfate and sodium nitrite
patent 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 nitrite

Method 5: oxidation of ethyl amine with peracids  (m-perbenzoicacid)
See Method 21:

Method 6: oxidation of ethyl amine with potassium permanganate
See Method 21:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0845

Method 7:  destructive distillation of alpha-bromopropionic acid with sodium nitrite
Synthesis of alpha-bromopropionic acid

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1p0115

Method 8:  oxidation of ethyl amine to nitroethane with dimethyldioxirane

Method 9:  isomerization of ethyl nitrite to nitroethane over asbestos catalyst

Method 10: ethyl bromide, DMSO, NaNO2 and phloroglucinol dihydrate
Preparation of Phloroglucinol

Post 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 NaNO2
Originally found by WizardX, but Joyman posted the method details

Post 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 synth

Method 13:  electrochemical oxidation ---- not possible by method below

Method 14, 15 and 16:  Vapor Phase nitration of propane, ethane and ethanol respectively
Other 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 DMSO

Patent 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 decarboxylation

Method 19:  Reduction of acetaldehyde oxime and oxidation of the product

Method 20: reduction of nitroethene to nitroethane using 2-phenylbenzimidazoline

Method 21: Oxidation of ethyl amine
Nitroethane 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 6
Oxidation via H₂O₂:
Oxidation with Peracids acid (Buffered and not):
The above is just like Method 5
Oxidation 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 nitrate
J.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 instead

Post 2716 (missing)

(psyloxy: "nitroethene", Chemistry Discourse)
Vapor-phase Nitromethane, formaldehyde over catalyst

Post 216189 (missing)

(halfapint: "Nitroethene Reduction to Nitroethane", Chemistry Discourse)
Dehydration of Nitroethanol
no 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 perborate

Post 435910 (missing)

(Lego: "Oximes to nitro alkanes with sodium perborate", Chemistry Discourse)

Method 26:  Oxidation of acetaldoxime with Oxone in MeCN

Post 435890 (missing)

(Lego: "Oxidation of oximes to nitroalkanes", Chemistry Discourse)

Method 27:  Oxidation of acetaldoxime with peroxytrifluoroacetic acid
J. Am. Chem. Soc., 1955, 77, 4557

Method 28: Oxidation of acetaldoxime with Urea-H₂O₂ complex in MeCN
Tet. Lett, 1992, 33, 4835

Method 29:  Oxidation of acetaldoxime with Benz-Mo in MeCN
Synlett, 1996, 1093

Method 30: Direct Nitration of Ethane (alkanes) with Nitronium Hexafluorophosphate

Post 471835

(pHarmacist: "Direct Nitration of Alkanes", Chemistry Discourse)

Method 31: Ethyl Halide to Nitroethane w/PTC

Post 474349

(Lego: "Nitroalkanes from bromoalkanes with PTC", Chemistry Discourse)


References for various methods given above:

Post 474663

(Rhodium: "original nitroethane literature", Methods Discourse)