ELECTROLYTIC PRODUCTION OF gem-DINITROPARAFFINS

Bahner, Carl Tabb

doi:10.1021/ie50506a028

Cited by 20 publications

(17 citation statements)

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“…Poor yield was observed confirming previously reported results [7,8]. The use of mediator couples Ag + /Ag 0 or Fe(CN) 6 -3/-4 improved 1,1-DNE yield dramatically and allowed the electrochemical reaction to run at much lower cell potentials. It is anticipated that the reaction pathway for the mediated electrochemical reaction investigated in this work is identical to the reaction paths studied previously [3,4], with the electrode serving as a regenerator of the oxidant species.…”

Section: Introductionsupporting

confidence: 87%

“…Oxidative nitration reactions have been shown to be sensitive to the oxidant, possibly due to formation of a complex which enables electron transfer [4]. The two oxidants that are known to work well for this reaction are Ag + and Fe(CN) 6 -3 [3,4]. Without formation of the complex, the energy barrier for this reaction requires higher electrochemical potentials, which in turn gives rise to undesirable side reactions.…”

Section: Mediator-based Electrolysismentioning

confidence: 99%

“…Common chemical oxidants used to drive the oxidative nitration reaction have been Ag + [4] and later Fe(CN) 6 -3 [3]. Due to the issues of cost, a secondary oxidant, Na 2 S 2 O 8 , was employed [5].…”

Section: Introductionmentioning

confidence: 99%

“…Due to the issues of cost, a secondary oxidant, Na 2 S 2 O 8 , was employed [5]. The Na 2 S 2 O 8 regenerates spent Fe(CN) 6 -4 by oxidation back to the active Fe(CN) 6 -3 state; thus keeping active catalytic amounts of Fe(CN) 6 -3 available for reaction. The replacement of the chemical oxidants with an anode has the possibility of removing the need for chemical oxidants and reducing process and disposal costs.…”

Section: Introductionmentioning

confidence: 99%

“…The first attempt involved a direct oxidative nitration on a Pt anode of 2-nitropropane to 2,2-dinitropropane albeit with low yield [6]. That work was reported about 10 years before the chemical synthesis method was reported [4].…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical synthesis of 2,2-dinitropropanol

Lister

Fox

2007

J Appl Electrochem

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This paper describes electrochemical approaches to the synthesis of 2,2-dinitropropanol (DNPOH) and discusses the potential for pilot-plant scale synthesis. In this work, the anode of the electrochemical cell replaces the chemical oxidants used in the conventional synthesis for the purpose of reducing secondary waste and the consequent disposal cost. The electrosynthesis reactions described in this work use the common starting material, nitroethane (NE). The synthesis of the end-product DNPOH involves two steps: (1) electrochemical oxidative nitration (addition of a geminal NO 2 group); and, (2) condensation with formaldehyde. Electrochemical oxidation of NE was first attempted by direct oxidation on a Pt electrode surface resulting in low yield and significant generation of undesirable by-product. Alternatively, two different mediators were employed resulting in a dramatic improvement of yield for the oxidative nitration step. The two different mediators used, Ag + /Ag 0 and Fe(CN) 6 -3/-4 , were derived from the chemical oxidants known to perform the oxidative nitration. The Fe(CN) 6 -3/-4 mediator demonstrated the best promise for scale-up and industrial production due to the lower cost of the mediator and the solubility of the mediator lending it to greater ease-of-use in conventional electrochemical cell designs.

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Section: Introductionsupporting

confidence: 87%

Section: Mediator-based Electrolysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrochemical synthesis of 2,2-dinitropropanol

Lister

Fox

2007

J Appl Electrochem

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Nitroparaffins

Bollmeier¹

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Four nitroparaffins are commercially available. These four, nitromethane, nitroethane, 1‐nitropropane, and 2‐nitropropane, are medium‐boiling liquids which are excellent solvents for a wide variety organic compounds and polymers. Some physical properties of these nitroparaffins and a few higher mononitroparaffins and polynitro compounds are presented. The nitroparaffins can undergo a number of reactions which give them utility for synthesis of other compounds of commercial importance. These reactions are discussed. Of particular importance is their ability to form nitronate salts with alkalis. This reaction is the first step for the halogenation reaction, eg, for the synthesis of the fumigant chloropicrin, or the condensation with carbonyl compounds for the synthesis of nitro alcohols. Production of the four commercial nitroparaffins is by vapor‐phase nitration of propane with nitric acid. Some 41,000 t of mixed nitroparaffins can be produced annually. All the nitroparaffins are flammable liquids. Their principal hazard is by inhalation. Special attention is required for handling nitromethane because it can be detonated under certain circumstances. The bulk of nitroparaffin production is used for synthesis of other chemical products. Nitromethane is useful as a fuel in drag racing and model airplanes, however, and nitroethane and 1‐nitropropane see use as solvent in coatings.

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Shechter‐Kaplan Oxidative Nitration

2010

Comprehensive Organic Name Reactions and Reagents

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The general conversion of primary and secondary nitroparaffins into either vicinal or geminal dinitro compounds via the oxidative nitration with silver nitrate under basic conditions is generally referred to as the Shechter–Kaplan oxidative nitration. It has been reported that the Shechter–Kaplan oxidative nitration can be promoted by either an anionic or cationic oxidant, or performed under an electrochemical condition. This reaction proceeds smoothly in alkaline aqueous solution at 0–30°C in a pH range of 7.2–9.4. This reaction is especially useful for the preparation of secondary gem ‐dinitro compounds, by which the ter Meer reaction fails, as shown in the formation of α,α,ω,ω‐tetranitroalkanes. This reaction is useful for the preparation of aliphatic compounds containing multiple nitro groups, especially for the vicinal or geminal dinitro functionalities.

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ELECTROLYTIC PRODUCTION OF gem-DINITROPARAFFINS

Cited by 20 publications

References 0 publications

Electrochemical synthesis of 2,2-dinitropropanol

Electrochemical synthesis of 2,2-dinitropropanol

Nitroparaffins

Shechter‐Kaplan Oxidative Nitration

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