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Title: Heterogeneous Catalytic Oxidation of Amides to Imides by Manganese Oxides

Abstract

Herein, we report a one-step peroxide mediated heterogeneous catalytic oxidation of amides to imides utilizing a series of manganese oxides. Among them, Cs/Mn 2O 3 was found to be the most active catalyst for the selective partial oxidation of N-benzylbenzamide to diphenyl imide. We have been able to apply an optimized oxidation method to other aromatic substrates. The feasibility of using air as an oxidant, the heterogeneous nature, inexpensive catalytic materials, respectable turnover numbers, and chemoselectivity to imides make this methodology an attractive choice for functional group transformations of amides to imides.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [3];  [4];  [3]
  1. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry
  2. Univ. of Connecticut, Storrs, CT (United States). Inst. of Materials Science
  3. ExxonMobil Research and Engineering Company, Annandale, NJ (United States). Corporate Strategic Research
  4. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry. Inst. of Materials Science
Publication Date:
Research Org.:
Univ. of Connecticut, Storrs, CT (United States); ExxonMobil Research and Engineering Company, Annandale, NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); ExxonMobil Research and Engineering Company
OSTI Identifier:
1500003
Grant/Contract Number:  
FG02-86ER13622
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; porous materials

Citation Formats

Biswas, Sourav, Khanna, Harshul S., Nizami, Quddus A., Caldwell, Donald R., Cavanaugh, Katherine T., Howell, Amy R., Raman, Sumathy, Suib, Steven L., and Nandi, Partha. Heterogeneous Catalytic Oxidation of Amides to Imides by Manganese Oxides. United States: N. p., 2018. Web. doi:10.1038/s41598-018-31729-3.
Biswas, Sourav, Khanna, Harshul S., Nizami, Quddus A., Caldwell, Donald R., Cavanaugh, Katherine T., Howell, Amy R., Raman, Sumathy, Suib, Steven L., & Nandi, Partha. Heterogeneous Catalytic Oxidation of Amides to Imides by Manganese Oxides. United States. doi:10.1038/s41598-018-31729-3.
Biswas, Sourav, Khanna, Harshul S., Nizami, Quddus A., Caldwell, Donald R., Cavanaugh, Katherine T., Howell, Amy R., Raman, Sumathy, Suib, Steven L., and Nandi, Partha. Tue . "Heterogeneous Catalytic Oxidation of Amides to Imides by Manganese Oxides". United States. doi:10.1038/s41598-018-31729-3. https://www.osti.gov/servlets/purl/1500003.
@article{osti_1500003,
title = {Heterogeneous Catalytic Oxidation of Amides to Imides by Manganese Oxides},
author = {Biswas, Sourav and Khanna, Harshul S. and Nizami, Quddus A. and Caldwell, Donald R. and Cavanaugh, Katherine T. and Howell, Amy R. and Raman, Sumathy and Suib, Steven L. and Nandi, Partha},
abstractNote = {Herein, we report a one-step peroxide mediated heterogeneous catalytic oxidation of amides to imides utilizing a series of manganese oxides. Among them, Cs/Mn2O3 was found to be the most active catalyst for the selective partial oxidation of N-benzylbenzamide to diphenyl imide. We have been able to apply an optimized oxidation method to other aromatic substrates. The feasibility of using air as an oxidant, the heterogeneous nature, inexpensive catalytic materials, respectable turnover numbers, and chemoselectivity to imides make this methodology an attractive choice for functional group transformations of amides to imides.},
doi = {10.1038/s41598-018-31729-3},
journal = {Scientific Reports},
number = ,
volume = 8,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 4 works
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Figures / Tables:

Table 1 Table 1: Optimization of oxidation of N-benzylbenzamide. aReaction conditions: N-benzyl benzamide (100 mg, 0.5 mmol, 1.0 equiv), meso Cs/Mn2O3 (50 mg), acetonitrile (5 mL, 95 mmol, 190 equiv), 80 °C, TBHP (5 mmol, 0.45 g, 10 equiv), 22 h. bConversions and selectivities were determined by GC-MS based on concentration ofmore » N-benzyl benzamide using m-xylene as internal standard. Isolated yields are in parentheses. cTBHP addition rate of 0.8 μL min−1. d10 mol% NHPI. eMolecular sieves as additives (200 mg) and air. fNo catalyst. nd = not detected by GC-MS.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.