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Title: A Convenient and Safer Synthesis of Diaminoglyoxime

A new procedure for the synthesis and isolation of diaminoglyoxime (DAG) is described. A previous procedure involved treating glyoxal with two equivalents each of hydroxylammonium chloride and sodium hydroxide to form glyoxime, followed by further treatment of this intermediate with two additional equivalents of hydroxylammonium chloride and sodium hydroxide at 95 °C to form DAG. Two recrystallizations were needed to obtain the desired product in pure form. Another previous procedure employed glyoxal in the presence of four equivalents each of hydroxylammonium chloride and sodium hydroxide at 95 °C to form DAG. Though this latter procedure gives product after a few hours, yields do not exceed 40%, and the reaction is prone to thermal runaway. Furthermore, the use of decolorizing carbon, and recrystallization of the crude solid is necessary to obtain a pure product. The new disclosed procedure involves treating a preheated aqueous hydroxylamine solution (50 wt. %, ten equivalents) with aqueous glyoxal (40 wt. %), followed by heating at 95 °C for 72-96 h. The reaction is cooled to room temperature, and then to 0-5 °C to obtain DAG in pure form, without recrystallization or decolorizing carbon in 77-80% yield. The exothermic nature of the reaction is also minimized bymore » this updated process.« less
Authors:
 [1] ; ORCiD logo [1] ; ORCiD logo [2]
  1. U.S. Army Research Lab., Aberdeen Proving Ground, MD (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
LLNL-JRNL-741164
Journal ID: ISSN 1083-6160
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Organic Process Research & Development
Additional Journal Information:
Journal Volume: 21; Journal Issue: 12; Journal ID: ISSN 1083-6160
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1430934

Johnson, Eric C., Sabatini, Jesse J., and Zuckerman, Nathaniel B.. A Convenient and Safer Synthesis of Diaminoglyoxime. United States: N. p., Web. doi:10.1021/acs.oprd.7b00329.
Johnson, Eric C., Sabatini, Jesse J., & Zuckerman, Nathaniel B.. A Convenient and Safer Synthesis of Diaminoglyoxime. United States. doi:10.1021/acs.oprd.7b00329.
Johnson, Eric C., Sabatini, Jesse J., and Zuckerman, Nathaniel B.. 2017. "A Convenient and Safer Synthesis of Diaminoglyoxime". United States. doi:10.1021/acs.oprd.7b00329. https://www.osti.gov/servlets/purl/1430934.
@article{osti_1430934,
title = {A Convenient and Safer Synthesis of Diaminoglyoxime},
author = {Johnson, Eric C. and Sabatini, Jesse J. and Zuckerman, Nathaniel B.},
abstractNote = {A new procedure for the synthesis and isolation of diaminoglyoxime (DAG) is described. A previous procedure involved treating glyoxal with two equivalents each of hydroxylammonium chloride and sodium hydroxide to form glyoxime, followed by further treatment of this intermediate with two additional equivalents of hydroxylammonium chloride and sodium hydroxide at 95 °C to form DAG. Two recrystallizations were needed to obtain the desired product in pure form. Another previous procedure employed glyoxal in the presence of four equivalents each of hydroxylammonium chloride and sodium hydroxide at 95 °C to form DAG. Though this latter procedure gives product after a few hours, yields do not exceed 40%, and the reaction is prone to thermal runaway. Furthermore, the use of decolorizing carbon, and recrystallization of the crude solid is necessary to obtain a pure product. The new disclosed procedure involves treating a preheated aqueous hydroxylamine solution (50 wt. %, ten equivalents) with aqueous glyoxal (40 wt. %), followed by heating at 95 °C for 72-96 h. The reaction is cooled to room temperature, and then to 0-5 °C to obtain DAG in pure form, without recrystallization or decolorizing carbon in 77-80% yield. The exothermic nature of the reaction is also minimized by this updated process.},
doi = {10.1021/acs.oprd.7b00329},
journal = {Organic Process Research & Development},
number = 12,
volume = 21,
place = {United States},
year = {2017},
month = {11}
}