Facile Esterification of Alcohols with 2-Acyl-4,5-dichloropyridazin-3(2H)-ones under Friedel–Crafts Conditions

Abstract

This paper describes the esterification of aromatic and aliphatic alcohols by using 2-acyl-4,5-dichloropyridazin-3(2H)-ones as an acyl source under Friedel–Crafts conditions. Twelve alcohols were reacted with four 2-acyl-4,5-dichloropyridazin-3(2H)-ones in the presence of AlCl₃ in tetrahydrofuran at room temperature to give the corresponding esters in moderate to excellent yields. Thus, 2-acylpyridazin-3(2H)-ones serve as good and atom-economic acyl sources for the esterification of aromatic alcohols under Friedel–Crafts conditions, representing a rapid, practical, and efficient method of esterification.

Key words

acylation - esterification - Friedel–Crafts condition - sustainable chemistry - synthetic methods

• References and Notes

• 1 Larock RC. Comprehensive Organic Transformations . VCH; New York, NY: 1989: 966
• 2 Katrizky AR, Meth CO, Charles WR. Comprehensive Organic Functional Group Transformations . Vol. 5. Pergamon; Cambridge, UK: 1995: 122
• 3 Fischer E, Speier A. Ber. Dtsch. Chem. Ges. 1895; 28: 3252
• 4a Hangx, G.; Kwant, G.; Maessen, H.; Markusse, P.; Urseanu, I. Reaction Kinetics of the Esterification of Ethanol and Acetic Acid Towards Ethyl Acetate, Deliverable 22, Intelligent Column Internals for Reactive Separations (INTINT), Technical Report to the European Commission, http://www.cpi.umist.ac.uk/intint/NonConf_Del/22.pdf (2001).
• 4b Zhang G.-S. Synth. Commun. 1998; 28: 1159
• 5a Ishihara K, Nakayama M, Ohara S, Yamamoto H. Tetrahedron 2002; 58: 8179
• 5b Ishihara K, Nakagawa S, Sakakura A. J. Am. Chem. Soc. 2005; 127: 4168
• 5c Chen C.-T, Munot YS. J. Org. Chem. 2005; 70: 8625
• 5d Chakraborti AK, Singh B, Chankeshwara SV, Patel AR. J. Org. Chem. 2009; 74: 5967
• 5e Barrett AG. M, Braddock DC. Chem. Commun. 1997; 351
• 5f Srinivas KV. N. S, Mahender I, Das B. Synthesis 2003; 2479
• 5g Sharghi H, Hosseini Sarvari M. Tetrahedron 2003; 59: 3627
• 5h Moumne R, Lavielle S, Karoyan P. J. Org. Chem. 2006; 71: 3332

For selected examples, see:
• 6a Mackay LG, Wylie RS, Sanders JK. J. Am. Chem. Soc. 1994; 116: 3141
• 6b Gianneschi NC, Nguyen ST, Mirkin CA. J. Am. Chem. Soc. 2005; 127: 1644
• 6c Yoon HJ, Mirkin CA. J. Am. Chem. Soc. 2008; 130: 11590
• 6d Neises B, Steglich W. Angew. Chem., Int. Ed. Engl. 1978; 17: 522

For selected examples, see:
• 7a Ohta S, Shimabayashi A, Aono M, Okamoto M. Synthesis 1982; 833
• 7b Maseguer JD, Coll AL. P, Lizarbe JR. F, Bilbao AZ. Synthesis 1980; 547
• 7c Kim S, Lee JI, Ko YK. Tetrahedron Lett. 1984; 25: 4943
• 7d Nahmany M, Melman A. Org. Lett. 2001; 3: 3733
• 7e Saitoh K, Shiina I, Mukaiyama T. Chem. Lett. 1988; 679
• 7f Candrasekaran S, Tumer JV. Synth. Commun. 1982; 12: 727
• 7g Mukaiyama T, Ichikawa J, Asami M. Chem. Lett. 1983; 683
• 7h Ramaiah M. J. Org. Chem. 1985; 50: 4991
• 7i Shiina I, Miyoshi S, Miyashita M, Mukaiyama T. Chem. Lett. 1994; 515
• 7j Kunishima M, Kawach C, Hioki K, Terao K, Tani S. Tetrahedron 2001; 57: 1551
• 7k Wakasugi K, Nakamura A, Tanabe Y. Tetrahedron Lett. 2001; 42: 7427
• 7l Shiina I, Kubota M, Oshiumi H, Hashizume M. J. Org. Chem. 2004; 69: 1822
• 7m Wakasugi K, Iida A, Misaki T, Nishii Y, Tanabe Y. Adv. Synth. Catal. 2003; 345: 1209
• 8 For some examples, see refs. 7d and 7j–m. See also: Anastas PT, Kirchhoff MM. Acc. Chem. Res. 2002; 35: 686
• 9 Constable DJ. C, Dunn PJ, Hayler JD, Humphrey GR, Leazer JL, Linderman RJ. Jr, Lorenz K, Manley J, Pearlman BA, Wells A, Zaks A, Zhang TY. Green Chem. 2007; 9: 411
• 10a Sartori G, Maggi R. Chem. Rev. 2006; 106: 1077
• 10b Chaube VD, Moreau P, Finiels A, Ramaswamy AV, Singh AP. J. Mol. Catal. A: Chem. 2001; 174: 255
• 10c Oulsanjo MS, Cartledge T, Shah K, Ahmed S. Lett. Drug Des. Discovery 2011; 8: 253
• 10d Hocking MB. J. Chem. Technol. Biotechnol. 1980; 30: 626
• 11a Kim BR, Sung GH, Ryu KE, Kim JJ, Yoon YJ. Bull. Korean Chem. Soc. 2013; 34: 3410
• 11b Kim BR, Sung GH, Lee SG, Yoon YJ. Tetrahedron 2013; 69: 3234
• 12a Sung GH, Kim BR, Lee SG, Kim JJ, Yoon YJ. Curr. Org. Chem. 2012; 16: 852
• 12b Lee SG, Kim JJ, Kim HK, Kweon DH, Kang YJ, Cho SD, Kim SK, Yoon YJ. Curr. Org. Chem. 2004; 8: 1463
• 12c Kang YJ, Chung H.-A, Kim JJ, Yoon YJ. Synthesis 2002; 733
• 13a Chung H.-A, Kim JJ, Cho SD, Lee SG, Yoon YJ. J. Heterocycl. Chem. 2002; 39: 685
• 13b Cho SD, Park YD, Kim JJ, Joo WH, Shiro M, Esser L, Falck JR, Ahn C, Shin DS, Yoon YJ. Tetrahedron 2004; 60: 3763
• 14a Synthesis of 3 and 5a–d; General Procedure: To a solution of alcohol 2 (1 equiv, 2 mmol) in THF (20 mL), AlCl₃ (1 equiv) was added followed by stirring for 1 min. 2-Acyl-4,5-pyridazin-3(2H)-one 1 (1 equiv) was then added and the mixture was stirred at room temperature until the alcohol was consumed. The reaction was quenched by the addition of H₂O (20 mL), and the mixture was stirred for 10 min at room temperature. After the addition of CH₂Cl₂ (40 mL), the organic layer was separated and dried over anhydrous MgSO₄. The solvent was evaporated under reduced pressure, and the resulting residue was applied to the top of an open-bed silica gel column. The column was eluted with CH₂Cl₂ (for 3a–g, 5a and 5b), MeCN–CH₂Cl₂ (1:5 v/v for 3h), EtOAc–CH₂Cl₂ (1:1 v/v for 3i), n-hexane–CH₂Cl₂–EtOAc (4:2:1 v/v for 3j and 3k), or n-hexane–EtOAc (10:1 v/v for 5c and 5d). Fractions containing the product were combined and evaporated under reduced pressure to give the desired esters. Fractions containing 4,5-dichloropyridazin-3(2H)-one were combined and evaporated under reduced pressure to quantitatively give reusable 4,5-dichloropyridazin-3(2H)-one. (b) Synthesis of 5e–i; General Procedure: To a solution of alcohol 2 (1 equiv, 2 mmol) in THF (20 mL), AlCl₃ (1 equiv) was added followed by stirring for 1 min. 2-Aroyl-4,5-dichloropyridazin-3(2H)-one 1 (1 equiv) was added and the mixture was stirred at room temperature until the alcohol was consumed. The reaction was quenched by the addition of H₂O (20 mL), followed by stirring for 10 min at room temperature, and then neutralized with a saturated solution of NaHCO₃. After the addition of further H₂O (20 mL) and CH₂Cl₂ (40 mL), the resulting organic layer was separated, and H₂O (10 mL) and a saturated solution of NaCl (20 mL) were added. The organic layer was then separated and dried over anhydrous MgSO₄. The solvent was evaporated under reduced pressure and the resulting residue was applied to the top of an open-bed silica gel column. The column was eluted with CH₂Cl₂ (for 5g–i) or n-hexane–EtOAc (3:1 v/v for 5e and 5f). Fractions containing the product were combined and evaporated under reduced pressure to give the desired esters. Fractions containing 4,5-dichloropyridazin-3(2H)-one were combined and evaporated under reduced pressure to quantitatively give reusable 4,5-dichloropyridazin-3(2H)-one.
• 15 Procedures for Methods A–E in Scheme 3 Method A: To a solution of 1a (1 equiv) in THF (20 mL), 2b (1 equiv, 2 mmol) was added followed by stirring for 5 min. AlCl₃ (1 equiv) was added and the mixture was stirred for 10 min at room temperature. Method B: To a solution of 2b (1 equiv, 2 mmol) in THF (20 mL), AlCl₃ (1 equiv) was added followed by stirring for 30 min. 1a (1 equiv) was added and the mixture was stirred for 10 min at room temperature. Method C: To a solution of 1a (1 equiv) in THF (20 mL), AlCl₃ (1 equiv) was added followed by stirring for 30 min. 2b (1 equiv, 2 mmol) was added and the mixture was stirred for 10 min at room temperature. Method D: To a solution of 2b (1 equiv, 2 mmol) in THF (20 mL), AlCl₃ (1 equiv) was added followed by stirring for 30 min at room temperature. The solvent was evaporated under reduced pressure to give ROH–AlCl₃ adducts. After drying by vacuum pump for 1 h at room temperature, the adduct was used without further purification. Crude salt was dissolved in THF (20 mL), 1a (1 equiv) was added, and the mixture was stirred at room temperature at 10 min. Method E: To a solution of 1a (1 equiv) in THF (20 mL), AlCl₃ (1 equiv) was added followed by stirring for 30 min at room temperature. The solvent was evaporated under reduced pressure to give 1a–AlCl₃ adducts. After drying by vacuum pump for 1 h at room temperature, the adduct was used without further purification. Crude salt was dissolved in THF (20 mL), 2b (1 equiv 2 mmol) was added, and the mixture was stirred at room temperature at 10 min.