Ceric ammonium nitrate and manganese(III) acetate mediated radical oxidation and addition reactions of anthracene and 9-substituted anthracenes

2012 ◽  
Vol 31 (1) ◽  
pp. 55 ◽  
Author(s):  
Mustafa Zengin ◽  
Faith Sonmez ◽  
Mustafa Arslan ◽  
Mustafa Kucukislamoglu
Keyword(s):  
Ammonium Nitrate ◽  
Acidic Medium ◽  
Ceric Ammonium Nitrate ◽  
High Yield ◽  
Addition Reactions ◽  
Dimethyl Malonate ◽  
Radical Oxidation ◽  
Anthraquinone Derivatives ◽  
Anthracene Derivatives

Radical oxidation and addition reactions of anthracene (1), 9-methylanthracene (2) and 9-phenylanthracene (3) were investigated with dimethyl malonate (4) in the presence of ceric ammonium nitrate (CAN) and manganese(III) acetate (Mn(OAc)3). Although mostly anthraquinone derivatives and bianthrone were obtained with CAN, substituted 9,10-dihydroanthracene and 9,10-substituted anthracene derivatives were obtained with Mn(OAc)3. Dimethylmalonyl addition products (5a, 33 % and 5b, 42 %) were obtained in higher yield than quinones (5d, 8 % and 5e, 3 %) using Mn(OAc)3 as oxidant. 9a (96 %) and 9b (84 %) were synthesized in high yield and substitution products (7a, 44 % and 8b, 56 %) were obtained in higher yields than quinones (5d and 5e) using CAN as oxidant. The reactions were carried out in non-acidic medium (dichloromethane and methanol). Based on the structures of the isolated products a mechanism for these transformations was proposed.

Radical Oxidation of 17-Functionalized 14α-Hydroxy Steroids

2001 ◽  
Vol 66 (12) ◽  
pp. 1764-1776 ◽  
Author(s):  
Vladimir A. Khripach ◽  
Vladimir N. Zhabinskii ◽  
Anna I. Kotyatkina ◽  
Galina P. Fando ◽  
Yuliya Y. Zhiburtovich ◽  
...  
Keyword(s):  
Ammonium Nitrate ◽  
Functional Groups ◽  
Lead Tetraacetate ◽  
Complex Mixtures ◽  
Ceric Ammonium Nitrate ◽  
Radical Oxidation ◽  
X Ray ◽  
Oxidizing Agents

The radical oxidation of 14α-hydroxy steroids with various functional groups at C-17 was studied. Lead tetraacetate and ceric ammonium nitrate were used as oxidizing agents. It was shown that reactions of this type afforded complex mixtures of compounds. However, the radical oxidation of 14α-hydroxy-17-oxo steroid (lead tetraacetate version of the hypoiodite reaction) proceeded smoothly with formation of the 13,14-secosteroid in up to 85% yield. The structure and conformation of the formed 13α-iodo-3α,5-cyclo-13,14-seco-5α-androst-5-ene-14,17-dione was determined by X-ray analysis.

scholarly journals Recoverable Phospha-Michael Additions Catalyzed by a 4-N,N-Dimethylaminopyridinium Saccharinate Salt or a Fluorous Long-Chained Pyridine: Two Types of Reusable Base Catalysts

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1159
Author(s):  
Eskedar Tessema ◽  
Vijayanath Elakkat ◽  
Chiao-Fan Chiu ◽  
Jing-Hung Zheng ◽  
Ka Long Chan ◽  
...  
Keyword(s):  
Michael Addition ◽  
Polar Solvent ◽  
Addition Reaction ◽  
High Yield ◽  
Addition Reactions ◽  
Polar Solvents ◽  
Unsaturated Bond ◽  
Base Catalysts ◽  
Michael Additions

Phospha-Michael addition, which is the addition reaction of a phosphorus-based nucleophile to an acceptor-substituted unsaturated bond, certainly represents one of the most versatile and powerful tools for the formation of P-C bonds, since many different electrophiles and P nucleophiles can be combined with each other. This offers the possibility to access many diversely functionalized products. In this work, two kinds of basic pyridine-based organo-catalysts were used to efficiently catalyze phospha-Michael addition reactions, the 4-N,N-dimethylaminopyridinium saccharinate (DMAP·Hsac) salt and a fluorous long-chained pyridine (4-Rf-CH2OCH2-py, where Rf = C11F23). These catalysts have been synthesized and characterized by Lu’s group. The phospha-Michael addition of diisopropyl, dimethyl or triethyl phosphites to α, β-unsaturated malonates in the presence of those catalysts showed very good reactivity with high yield at 80–100 °C in 1–4.5 h with high catalytic recovery and reusability. With regard to significant catalytic recovery, sometimes more than eight cycles were observed for DMAP·Hsac adduct by using non-polar solvents (e.g., ether) to precipitate out the catalyst. In the case of the fluorous long-chained pyridine, the thermomorphic method was used to efficiently recover the catalyst for eight cycles in all the reactions. Thus, the easy separation of the catalysts from the products revealed the outstanding efficacy of our systems. To our knowledge, these are good examples of the application of recoverable organo-catalysts to the DMAP·Hsac adduct by using non-polar solvent and a fluorous long-chained pyridine under the thermomorphic mode in phospha-Michael addition reactions.

ChemInform Abstract: Oxidation of 4-methoxyanilines to 1,4-Benzoquinones Using Ceric Ammonium Nitrate (CAN).

ChemInform ◽  
2011 ◽  
Vol 42 (15) ◽  
pp. no-no
Author(s):  
Yugang Chen ◽  
Weijiang Ying ◽  
Michael Harmata
Keyword(s):  
Ammonium Nitrate ◽  
Ceric Ammonium Nitrate

OXIDATIVE REMOVAL OFN-(p-METHOXYBENZYL) GROUP ON DIKETOPIPERAZINE SKELETON WITH CERIC AMMONIUM NITRATE

1983 ◽  
Vol 12 (7) ◽  
pp. 1001-1002 ◽  
Author(s):  
Juji Yoshimura ◽  
Masanori Yamaura ◽  
Tsuneji Suzuki ◽  
Hironobu Hashimoto
Keyword(s):  
Ammonium Nitrate ◽  
Ceric Ammonium Nitrate ◽  
Oxidative Removal
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