Phosphorus Oxychloride

Introduction

Phosphorus oxychloride (POCl₃) is a common and intensively used inorganic compound industrially prepared from phosphorus trichloride either by oxidation with oxygen or chlorination followed by treatment with phosphorus pentoxide (Scheme  [¹] ). Despite it reacts violently with water, this stable colorless liquid has been extensively studied for decades to promote the synthesis of diverse heterocycles, [¹] such as the Bischler-Napieralski formation of isoquinolines [²] and its related cyclisations [³] , the Meth-Cohn approach to quinolines [4] or the Robinson-Gabriel route to oxazole. [5] Beyond the heterocyclic chemistry, phosphorus oxychloride is a powerful reagent for various functionalization like chlorinations, [6] Vilsmeier-Haack formylations [7] or dehydratations. [8] POCl₃ also appears as a key reagent in bioorganic chemistry to phosphorylate proteins [9] or nucleosides, [¹0] and enters in the preparation of some polymers. [¹¹]

Scheme 1  Industrial preparation of phosphorus oxychloride

References

• 1 Sharma SD. Kanwar S. Indian J. Chem., Sect B: Org. Chem. Incl. Med. Chem.  1998,  37, 965 
• 2a Gensler WJ. Org. React.  1951,  74 
• 2b Awuah E. Capretta A. J. Org. Chem.  2010,  75:  5627 
• 3a Chrzanowska M. Rozwadowska MD. Chem. Rev.  2004,  104:  3341 
• 3b Bronstein HA. Finlayson CE. Kirov KR. Friend RH. Williams CK. Organometallics  2008,  27, 2980 
• 4a Meth-Cohn O. Heterocycles  1993,  35, 539 
• 4b Baruah B. Bhuyan PJ. Tetrahedron  2009,  65, 7099 
• For examples, see:
• 5a Gammon DW. Hunter R. Seanette AW. Tetrahedron  2005,  61:  10683 
• 5b Miyake F. Hashimoto M. Tonsiengsom S. Yakushijin K. Horne DA. Tetrahedron  2010,  66, 4888 
• For examples, see:
• 6a Cailly T. Begtrup M. Tetrahedron  2010,  66:  1299 
• 6b Shing TKM. Cheng HM. J. Org. Chem.  2010,  75, 3522 
• 7a Jones G. Stanforth SP. Org. React.  2001,  49:  1 
• 7b Quiroga J. Diaz Y. Insuasty B. Abonia R. Nogueras M. Cobo J. Tetrahedron Lett.  2010,  51:  2928 
• For examples, see:
• 8a Yin Y. Zhang Q. Liu Q. Liu Y. Sun S. Synth. Commun.  2007,  37:  730 
• 8b Shavaev KV. Tandon SS. Dawe LN. Thompson LK. Chem. Commun.  2010,  46, 4755 
• For examples, see:
• 9a Nayak SK. Arora S. Sindhu JS. Sangwan RB. Int. Dairy J.  2006,  16:  268 
• 9b Han J.-A. BeMiller JN. Carbohydr. Polym.  2008,  73:  532 
• For examples, see:
• 10a Wridges CT. Timper J. Fischler M. Sologubenko AS. Mayer J. Simon U. Carell T. Angew. Chem. Int. Ed.  2009,  48:  219 
• 10b Liu M. Jinmei H. Abe H. Ito Y. Bioorg. Med. Chem. Lett.  2010,  20, 2964 
• For examples, see:
• 11a Anwar E. Khotimah H. Yanuar A. J. Med. Sci.  2006,  6, 923 
• 11b Wang X. Hu Y. Song L. Xing W. Lu H. Lv P. Jie G. Polymer  2010,  51:  2435 
• 12 Zhang X. Lin Q. Zhong P. Molecules  2010,  15:  3079 
• 13a Gilbert AM. Nowak P. Brooijmans N. Bursavich MG. Dehnhardt C. Santos ED. Feldberg LR. Hollander I. Kim S. Lombardi S. Bioorg. Med. Chem. Lett.  2010,  20:  636 
• 13b Ghorab MM. Ragab FA. Alqasoumi SI. Alafeefy AM. Aboulmagd SA. Eur. J. Med. Chem.  2010,  45:  171 
• 14 Li K.-L. Du Z.-B. Guo C.-C. Chen Q.-Y. J. Org. Chem.  2009,  74:  3286 
• 15 Rida SM. Ashour FA. El-Hawash SAM. Elsemary SS. Badir MH. Shalaby MA. Eur. J. Med. Chem.  2005,  40:  949 
• 16 Meesala R. Nagarajan R. Tetrahedron Lett.  2010,  51:  422 
• 17 Harvey JS. Giuffredi GT. Gouverneur V. Org. Lett.  2010,  12, 1236 
• 18 Akritopoulou-Zanze I. Gracias V. Moore JD. Djuric SW. Tetrahedron Lett.  2004,  45:  3421 
• 19 Gopinath C. Thomas S. Nair MS. Ibnusaud I. Tetrahedron Lett.  2006,  47:  7957 
• 20 Meshram J. Ali P. Tiwari V. J. Heterocycl. Chem.  2010,  47:  1454