Esterification of Aldehydes and Alcohols with Pyridinium Hydrobromide Perbromide in Water

Abstract

The direct esterification of aldehydes and alcohols was carried out with pyridinium hydrobromide perbromide in water at room temperature. A variety of aldehydes were converted to respective ester derivatives with alcohols such as methanol, 1,2-ethanediol, 1,3-propanediol. Further, a variety of aliphatic alcohols were also converted to the corresponding Tishchenko-like dimeric esters in good yields under the same reaction conditions.

Key words

esterification - water - pyridinium hydrobromide perbromide - aldehyde - alcohol

References

• 1a Larock RC. In Comprehensive Organic Transformation   Wiley-VCH; New York: 1999. 
• 1b Ho T.-L. Fiesers’ Reagents for Organic Synthesis   Vol. 1-21:  Wiley; New York: 1967-2003. 
• 1c Naik S. Gopinath R. Goswami M. Patel BK. Org. Biomol. Chem.  2004,  2:  1670 
• 1d Gopinath R. Haque SK. Patel BK. J. Org. Chem.  2002,  67:  5842 
• 1e Naik S. Gopinath R. Patel BK. Tetrahedron Lett.  2001,  42:  7679 
• 1f Gopinath R. Patel BK. Org. Lett.  2000,  2:  4177 
• 1g Bora U. Bose G. Chaudhuri MK. Dhar SS. Gopinath R. Khan AT. Patel BK. Org. Lett.  2000,  2:  247 
• 2a Dessolin J. Biot C. Davioud-Charvet E. J. Org. Chem.  2001,  66:  5616 
• 2b Chaudhuri MK. Khan AT. Patel BK. Dey D. Kharmawophlang W. Lakshmiprabha TR. Mandal GC. Tetrahedron Lett.  1998,  39:  8163 
• 2c Collado IG. Galan RH. Massanet GM. Alonso MS. Tetrahedron  1994,  50:  6433 
• 2d Baraldi PG. Bazzanini R. Manfredini S. Simoni D. Robins MJ. Tetrahedron Lett.  1993,  34:  3177 
• 2e Reeves WP. King RM. Synth. Commun.  1993,  23:  855 
• 2f Husstedt U. Schafer HJ. Synthesis  1979,  966 
• 3a Qian G. Zhao R. Ji D. Lu G. Qi Y. Suo J. Chem. Lett.  2004,  33:  834 
• 3b Gopinath R. Barkakaty B. Talukdar B. Patel BK. J. Org. Chem.  2003,  68:  2944 
• 3c Sharghi H. Sarvari MH. J. Org. Chem.  2003,  68:  4096 
• 3d Gopinath R. Patel BK. Org. Lett.  2000,  2:  577 
• 3e Espeson JH. Zhu Z. Zauche TH. J. Org. Chem.  1999,  64:  1191 
• 3f Gregg PJ. Olsson L. Oscarson S. J. Org. Chem.  1995,  60:  2200 
• 3g Stowell JC. Ham BM. Esslinger MA. Duplantier AJ. J. Org. Chem.  1989,  54:  1212 
• 3h Okimoto M. Chiba T. J. Org. Chem.  1988,  53:  218 
• 3i Wilson SR. Tofigh S. Misra RN. J. Org. Chem.  1982,  47:  1360 
• 3j Stevens RV. Chapman KT. Stubbs CA. Tam WW. Albizati KF. Tetrahedron Lett.  1982,  23:  4647 
• 3k Nwaukwa SO. Keehn PM. Tetrahedron Lett.  1982,  23:  35 
• 3l Pinnick HW. Lajis NH. J. Org. Chem.  1978,  43:  371 
• 3m Sundararaman P. Walker EC. Djerassi C. Tetrahedron Lett.  1978,  1627 
• 3n Ogawa T. Matsui M. J. Am. Chem. Soc.  1976,  98:  1629 
• 3o Corey EJ. Gilman NW. Ganem BE. J. Am. Chem. Soc.  1968,  90:  5616 
• 5a Saitoh K. Shiina I. Mukaiyama T. Chem. Lett.  1998,  679 
• 5b Brinchi L. Germani R. Savelli G. Tetrahedron Lett.  2003,  44:  6583 
• 5c Zander N. Gerhardt J. Frank R. Tetrahedron Lett.  2003,  44:  6557 
• 5d Enholm EJ. Bhardawaj A. Tetrahedron Lett.  2003,  44:  3763 
• 5e Gacem B. Jenner G. Tetrahedron Lett.  2003,  44:  1391 
• 5f Pan W.-B. Chang F.-R. Wei L.-M. Wu M.-J. Wu Y.-C. Tetrahedron Lett.  2003,  44:  331 
• 5g Jang DO. Cho DH. Kim J.-G. Synth. Commun.  2003,  33:  2885 
• 5h Karade NN. Shirodkar SG. Potrekar RA. Karade HN. Synth. Commun.  2004,  34:  391 
• 6a Reis MG. Faria AD. Amaral MCE. Marsaioli AJ. Tetrahedron Lett.  2003,  44:  8519 
• 6b Ueki T. Morimoto Y. Kinoshita T. J. Chem. Soc., Chem. Commun.  2001,  1820 
• 6c Hisamatsu Y. Goto N. Hasegawa K. Shigemori H. Tetrahedron Lett.  2003,  44:  5553 
• 6d Schulz T. Eicher T. Synthesis  2003,  1253 
• 9 Yunker MB. Fraser-Reid B. J. Chem. Soc., Chem. Commun.  1975,  61 
• 10 Guo Z. Padmakumar R. Hollingsworth RI. Radhakrishnan KV. Nandakumar MV. Fraser-Reid B. Synlett  2003,  1067 
• 11 Ermolenko L. Sasaki NA. Potier P. Synlett  2001,  1565 
• 12 Kageyama T. Ueno Y. Okawara M. Synthesis  1983,  815 
• 13 Masuyama Y. Takahashi M. Kurusu Y. Tetrahedron Lett.  1984,  25:  4417 
• 14 Dauben WG. Warshawsky AM. Synth. Commun.  1988,  18:  1323 
• 16 Tanaka H. Kawakami Y. Goto K. Kuroboshi M. Tetrahedron Lett.  2001,  42:  445 
• 17 Shaabani A. Lee DG. Tetrahedron Lett.  2001,  42:  5833 
• 18 Morimoto T. Hirano M. Iwasaki K. Ishikawa T. Chem. Lett.  1994,  53 
• 19 Okimoto M. Nagata Y. Sueda S. Takahashi Y. Synth. Commun.  2004,  34:  281 
• 20 Hiegel GA. Gilly CB. Synth. Commun.  2003,  33:  2003 

4

4-Methylbenzoic acid was recovered in 88% yield at 2.0 molar equiv of PHPB and 16 molar equiv of ethylene glycol over 4-methylbenzoic acid in H₂O for 14 h.

7

The oxidation of 2-ethyl-1,3-hexanediol (18) containing both secondary and primary hydroxyl groups, was carried out with 2.0 molar equiv of PHPB over 18 in H₂O at r.t. for 75 h. Only the secondary 3-hydroxyl group of 18 was selectively oxidized to give hydroxyketone 19 in 82% yield (Table [6] , run 6).

8

Typical procedure for the Esterification of Iso butyraldehyde ( 4) and Dodecanol:
To a solution of PHPB (320 mg, 1.00 mmol) in H₂O (8 mL) were added 4 (36 mg, 0.50 mmol) and dodecanol (93 mg, 0.50 mmol). After stirring for 14 h at r.t., the reaction mixture was treated with 0.5 M aq Na₂S₂O₃ and extracted with EtOAc. The organic layer was washed with 0.5 M aq Na₂S₂O₃, successively sat. aq NaCl, and dried over MgSO₄. After removal of the solvent in vacuo, the residue was purified by column chromatography on silica gel (Wakogel C-200) with CCl₄ and CHCl₃ (3:1 v/v). Ester 4a (109 mg, 0.42 mmol) was obtained in 84% yield.

15

β-Phenylethylalcohol was recovered unchanged in 90% yield at a molar ratio of β-phenylethylalcohol, PHPB, pyridine (1:2:2) in H₂O for 18 h.

21

Typical Procedure for the Dimeric Esterification of Dodecanol ( 12): To a solution of PHPB (160 mg, 0.50 mmol) in H₂O (8 mL) was added 12 (46 mg, 0.25 mmol). After stirring for 13 h at r.t., the reaction mixture was treated with 0.5 M aq Na₂S₂O₃ and extracted with EtOAc. The organic layer was washed with 0.5 M aq Na₂S₂O₃, successively sat. aq NaCl, and_dried over MgSO₄. After removal of the solvent in vacuo, the residue was purified by column chromatography on silica gel (Wakogel C-200) with CCl₄. Dimeric ester 12a (44 mg, 0.12 mmol) was obtained in 95% yield.