A New Facile Route to Chlorination of Alcohols via Lewis Acid AlCl₃

Hengchang Ma, Zhikang Bao, Lianhua Bai, Wei Cao

Key Laboratory of Polymer Materials of Gansu Province, Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, China.

DOI: 10.4236/ijoc.2012.21004                

Abstract

Halogenated aluminates AlCl₃, applied as efficient chlorination reagent for hydroxyl groups of substitution alcohols is described. Primary and secondary benzylic alcohols could be transformed into corresponding aromatic halides with almost complete conversion and unique selectivity. As chlorination reagent, AlCl₃ has an incomparable advantage over others, such as low material cost, commercial availability as well as convenient product isolation.

Keywords

Alcohols; Lewis Acid; Nucleophiles; Chlorination

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	T. Hatakeyama, S. Ito, M. Nakamura and E. Nakamura, “Alky-lation of Magnesium Enamide with Alkyl Chlorides and Fluorides,” Journal of the American Chemical Society, Vol. 127, No. 41, 2005, pp. 14192-14193. doi:10.1021/ja055306q
[2]	D. C. Braddock and J. J.-P. Pey-ralans, “A General Synthesis of Five, Six and Seven-Membered Silasultones via Dehydrative Cyclisation,” Tetrahedron, Vol. 61, No. 30, 2005, pp. 7233-7240. doi:10.1016/j.tet.2005.05.042
[3]	M. Yasuda, Y. Onishi, M. Ueba, T. Miyai and A. Baba, “Direct Reduction of Alcohols: Highly Chemoselective Reducing System for Secondary or Tertiary Alcohols Using Chlorodiphenylsilane with a Catalytic Amount of Indium Trichloride,” Journal of Organic Chemistry, Vol. 66, 2001, pp. 7741-7744. doi:10.1021/jo0158534
[4]	M. Yasuda, T. Saito, M. Ueba and A. Baba, “Direct Substitution of the Hydroxy Group in Alcohols with Silyl Nucleophiles Catalyzed by Indium Trichloride,” Angewandte Chemie International Edition, Vol. 43, No. 11, 2004, pp. 1414-1416. doi:10.1002/anie.200353121
[5]	M. Yasuda, S. Yamasaki, Y. Onishi and A. Baba, “Indium-Catalyzed Direct Chlorination of Alcohols Using Chlorodimethylsilane-Benzil as a Selective and Mild System,” Journal of the American Chemical Society, Vol. 126, No. 23, 2004, pp. 7186-7187. doi:10.1021/ja048688t
[6]	G. Bringmann and S. Schneider, “Improved Methods for Dehydration and Hydroxy/Halogen Exchange Using Novel Combinations of Triphenylphosphine and Halogenated Ethanes,” Synthesis, 1983, pp. 139-141. doi:10.1055/s-1983-30255
[7]	R. M. Magid, O. S. Fruchey, W. L. Johnson and T. G. Allen, “Hexachloroace-tone/Triphenylphosphine: A Mild Reagent for the Regioselective and Stereospecific Production of Allylic Chlorides from the Alcohols,” Journal of Organic Chemistry, Vol. 44, No. 3, 1979, pp. 359-363. doi:10.1021/jo01317a011
[8]	D. O. Jang, D. J. Park and J. Kim, “A Mild and Efficient Procedure for the Preparation of Acid Chlorides from Carylic Acids,” Tetrahedron Letters, Vol. 40, No. 29, 1999, pp. 5323-5326. doi:10.1016/S0040-4039(99)00967-3
[9]	R. G. Weiss and E. I. Snyder, “Stereochemistry of Displacement Reactions at the Neopentyl Carbon. Further Observations on the Triphenyl-phosphine-Polyhalome- thane-Alcohol Reaction,” Journal of Organic Chemistry, Vol. 36, 1971, pp. 403-406. doi:10.1021/jo00802a009
[10]	T. Fujisawa, S. Iida and T. Sato, “A Convenient Method for the Transformation of Alcohols to Alkyl Chlorides Using N,N-Diphenylchlorophenylmethyleniminium Chlo- ride,” Chemistry Letters, Vol. 13, 1984, pp. 1173-1174. doi:10.1246/cl.1984.1173
[11]	T. Mukaiyama, S. I. Shoda and Y. Watanabe, “A New Synthetic Method for the Transformation of Alcohols to Alkyl Chlorides Using 2-Chlorobenzoxazolium Salt,” Chemistry Letters, Vol. 6, 1977, pp. 383-386. doi:10.1246/cl.1977.383
[12]	M. Benazza, R. Uzan, D. Beaupère and G. Demailly, “Direct Regioselective Chlorination of Unprotected Hexitols and Pentitols by Vilsmeier and Haack’s Salt,” Tetrahedron Letters, Vol. 33, No. 34, 1992, pp. 4901-4904. doi:10.1016/S0040-4039(00)61228-5
[13]	M. Benazza, R. Uzan, D. Beaupère and G. Demailly, “Direct Regioselective Chlorination of Unprotected Hexitols and Pentitols by Viehe’s Salt,” Tetrahedron Letters, Vol. 33, 1992, pp. 3129-3132. doi:10.1016/S0040-4039(00)79831-5
[14]	R. C. Larock, “Comprehensive Organic Transformations,” 2nd Edition, Wi-ley-VCH, New York, 1999, pp. 689-702.
[15]	J. E. Copen-haver and A. M. Whaley, “Organic Syntheses,” Wiley and Sons, New York, Vol. 1,1941, pp. 144-145.
[16]	E. S. Lewis and C. E Boozer, Journal of the American Chemical Society, Vol. 74, 1952, pp. 308-311.
[17]	R. E. Ireland, D. W. Norbeck, G. S. Mandel and N. S. Mandel, “Convergent Synthesis of Polyether Ionophore Antibiotics: An Approach to the Synthesis of the Monensin Tetrahydropyran-Bis(Tetrahydrofuran) via the Ester Enolate Claisen Rearrangement and Reductive Decarboxylation,” Journal of the American Chemical Society, Vol. 107, No. 11, 1985, pp. 3285-3294. doi:10.1021/ja00297a039
[18]	J. G. Lee and K. K. Kang, “Selenium Dioxide Catalyzed Conversion of Alcohols to Alkyl Chlorides by Chlorotrimethylsilane,” Journal of Organic Chemistry, Vol. 53, No. 15, 1988, pp. 3634-3637. doi:10.1021/jo00250a048
[19]	R. M. Magid, O. S. Fuchey and W. J. Johnson, “Hexachloroacetone/Triphenylphosphine: A Reagent for the Regio- and Stereoselective Conversion of Allylic Alcohols into Chlorides,” Tetrahedron Letters, Vol. 18, No. 35, 1977, pp. 2999-3002. doi:10.1016/S0040-4039(01)83138-5
[20]	T. T. Slage, T. T.-S. Huang and B. Franzus, “Mechanism of the Triphenylphos-phine-Tetrachloromethane-Alcohol Reaction: Pericyclic or Clustered Ion Pairs?” Journal of Organic Chemistry, Vol. 46, 1978, pp. 3526-3530. doi:10.1021/jo00330a030
[21]	P. J. Garegg, R. Johansson and B. Samuelsson, “Two Reagent Systems for Converting Hydroxy Compounds into Chlorides using the Triphenylphos-phine/Imidazole System,” Synthesis, Vol. 1984, No. 2, 1984, pp. 168-170. doi:10.1055/s-1984-30769
[22]	Z. Q. Lei and R. R. Wang, “Oxidation of Alcohols Using H2O2 as Oxidant Catalyzed by AlCl3. Baeyer-Villiger Oxidation of Ketones with Hydrogen Peroxide Catalyzed by Silica Supported Aluminum Chloride,” Catalysis Communications, Vol. 9, 2008, pp. 740-742. doi:10.1016/j.catcom.2007.08.012
[23]	Z. Q. Lei, L. L. Wei, R. R. Wang and G. F. Ma, “Baeyer-Villiger Oxidation of Ketones with Hydrogen Peroxide Catalyzed by Silica Supported Alu-minum Chloride,” Catalysis Communications, Vol. 9, No. 15, 2008, pp. 2467-2469. doi:10.1016/j.catcom.2008.06.022
[24]	J. J. Ritter and P. P. Minieri, “A New Reaction of Nitriles. I. Amides from Alkenes and Mononitriles,” Journal of the American Chemical Society, Vol. 70, 1948, pp. 4045-4048. doi:10.1021/ja01192a022
[25]	W. Pluempanupat and W. Chavasiri, “An Efficient Method for Chlorination of Alcohols Using PPh3/ Cl3CCONH2,” Tetrahedron Letters, Vol. 37, No. 51, 2006, pp. 6821-6823. doi:10.1016/j.tetlet.2006.07.060
[26]	L. D. Luca, G. Giacomelli and A. Porcheddu, “An Efficient Route to Alkyl Chlorides from Alcohols Using the Complex TCT/DMF,” Organic Letters, Vol. 4, No. 4, 2002, pp. 553-555. doi:10.1021/ol017168p
[27]	A. Dubey, A. K. Upadhyay and P. Kumar, “Pivaloyl Chloride/DMF: A New Reagent for Conversion of Alcohols to Chlorides,” Tetrahedron Letters, Vol. 51, No. 4, 2010, pp. 744-746. doi:10.1016/j.tetlet.2009.11.131