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Title: Environmentally Benign and Scalable Preparation of Diethyl Furoxan-3,4-dicarboxylate Using Silver Carbonate as a Nitrile Oxide Generator

Abstract

Diethyl furoxan-3,4-dicarboxylate (1) is a starting material for many heterocyclic compounds containing furoxan and furazan rings. Usually, furoxan 1 was prepared via a dimerization of corresponding nitrile oxide generated either by treatment of ethyl 2-chloro-2-(hydroxyimino)-acetate (2) with triethylamine or by nitration or conversion of α-activated ethyl acetate with acetyl nitrate in acetic acid or other catalytic reagents. Both methods are suitable for small-scale but suffered from various drawbacks for large-scale preparation. Years ago, a general method for the preparation of furoxan from corresponding hydroximidoyl chloride (R–CCl=NOH) with silver carbonate (Ag 2CO 3) was developed in our group. Now this method is extended to prepare 1 from 2. The synthesis involves the treatment of 2 with Ag 2CO 3 in THF at room temperature, with a 3–4 h reaction time, with a yield of 80–90%. Using this method, a one pound batch of the material has been prepared at the lab-scale, but the preparation should be easily scaled to the multikilogram synthesis. This is an environmentally benign process since the preparation generates little hazardous wastes due to the possible recycling of the solvent, THF, and the byproduct, silver chloride.

Authors:
ORCiD logo [1];  [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1566013
Report Number(s):
LLNL-JRNL-773016
Journal ID: ISSN 1083-6160; 964660
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Organic Process Research & Development
Additional Journal Information:
Journal Name: Organic Process Research & Development; Journal ID: ISSN 1083-6160
Publisher:
ACS Publications
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Mao-Xi, DeHope, Alan J., and Pagoria, Philip. F. Environmentally Benign and Scalable Preparation of Diethyl Furoxan-3,4-dicarboxylate Using Silver Carbonate as a Nitrile Oxide Generator. United States: N. p., 2019. Web. doi:10.1021/acs.oprd.9b00228.
Zhang, Mao-Xi, DeHope, Alan J., & Pagoria, Philip. F. Environmentally Benign and Scalable Preparation of Diethyl Furoxan-3,4-dicarboxylate Using Silver Carbonate as a Nitrile Oxide Generator. United States. doi:10.1021/acs.oprd.9b00228.
Zhang, Mao-Xi, DeHope, Alan J., and Pagoria, Philip. F. Fri . "Environmentally Benign and Scalable Preparation of Diethyl Furoxan-3,4-dicarboxylate Using Silver Carbonate as a Nitrile Oxide Generator". United States. doi:10.1021/acs.oprd.9b00228.
@article{osti_1566013,
title = {Environmentally Benign and Scalable Preparation of Diethyl Furoxan-3,4-dicarboxylate Using Silver Carbonate as a Nitrile Oxide Generator},
author = {Zhang, Mao-Xi and DeHope, Alan J. and Pagoria, Philip. F.},
abstractNote = {Diethyl furoxan-3,4-dicarboxylate (1) is a starting material for many heterocyclic compounds containing furoxan and furazan rings. Usually, furoxan 1 was prepared via a dimerization of corresponding nitrile oxide generated either by treatment of ethyl 2-chloro-2-(hydroxyimino)-acetate (2) with triethylamine or by nitration or conversion of α-activated ethyl acetate with acetyl nitrate in acetic acid or other catalytic reagents. Both methods are suitable for small-scale but suffered from various drawbacks for large-scale preparation. Years ago, a general method for the preparation of furoxan from corresponding hydroximidoyl chloride (R–CCl=NOH) with silver carbonate (Ag2CO3) was developed in our group. Now this method is extended to prepare 1 from 2. The synthesis involves the treatment of 2 with Ag2CO3 in THF at room temperature, with a 3–4 h reaction time, with a yield of 80–90%. Using this method, a one pound batch of the material has been prepared at the lab-scale, but the preparation should be easily scaled to the multikilogram synthesis. This is an environmentally benign process since the preparation generates little hazardous wastes due to the possible recycling of the solvent, THF, and the byproduct, silver chloride.},
doi = {10.1021/acs.oprd.9b00228},
journal = {Organic Process Research & Development},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {9}
}

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This content will become publicly available on September 13, 2020
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