The Chemistry of Cyclic Carbaphosphazenes: The First Observation of (R 2 PN)(ClCN) 2 ( R ═Cl, Ph) as a Reagent for the Conversion of Alcohols to Aldehydes, Ketones, and Alkyl Chlorides

Authors: Behera, Nabakrushna; Mishra, Pradyumna; Elias, Anil

Source: Phosphorus, Sulfur, and Silicon and the Related Elements, Volume 181, Number 10, October 2006 , pp. 2445-2452(8)

Publisher: Taylor and Francis Ltd

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Abstract:

The oxidation of nine primary and secondary alcohols to the corresponding aldehydes and ketones has been carried out under mild conditions and in good yields using the cyclocarbaphosphazenes (R 2 PN)(ClCN) 2 [R 2 P = Cl 2 P( 1 ), Ph 2 P( 2 )] along with dimethylsulfoxide. While both the P═Cl and C─Cl bonds of the carbaphosphazene can in principle bring about the reaction, we observed an increased preference for the C═Cl bonds over the P═Cl bonds in the oxidation of alcohol. Blocking the reactive P site on the heterocyclic ring with the phenyl groups was found to reduce the yields of the oxidized products, while blocking the C- sites with diethylamino groups resulted in no reaction. In addition, along with DMF, the same cyclocarbaphosphazene has been found to be useful for the conversion of alcohols to alkyl chlorides.

Keywords: Aldehydes; alkyl chlorides; cyclocarbaphosphazene; dimethylformamide; dimethyl sulfoxide; oxidation

Document Type: Research article

DOI: http://dx.doi.org/10.1080/10426500600733947

Affiliations: 1: Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi, India

Publication date: 2006-10-01