A Convenient Synthesis of Oxazolines and Imidazolines from Aromatic Aldehydes with Pyridinium Hydrobromide Perbromide in Water

Shinsei Sayama

doi:10.1055/s-2006-941597

LETTER

A Convenient Synthesis of Oxazolines and Imidazolines from Aromatic Aldehydes with Pyridinium Hydrobromide Perbromide in Water

Shinsei Sayama*
Department of Chemistry, Fukushima Medical University, Hikariga-oka, Fukushima 960-1295, Japan
Fax: +81(24)5471369; e-Mail: ssayama@fmu.ac.jp;

Abstract

Alle Artikel dieser Rubrik

Abstract

Various 2-oxazolines were prepared from aromatic aldehydes and 2-aminoethanol with pyridinium hydrobromide perbromide in water at room temperature. 2-Imidazolines were also obtained in good yields from aromatic aldehydes and ethylenediamine under the same reaction conditions.

Key words

oxazoline - imidazoline - pyridinium hydrobromide perbromide - aldehyde - 2-aminoethanol - ethylenediamine

Volltext

Referenzen

References and Notes

<A NAME="RU02006ST-1A">1a</A> Genet JP. Thorimbert S. Touzin AM. Tetrahedron Lett. 1993, 34: 1159

<A NAME="RU02006ST-1B">1b</A> Wipf P. Venkatraman S. Synlett 1997, 1

<A NAME="RU02006ST-1C">1c</A> Mohammadpoor-Baltork I. Khosropour AR. Hojati SF. Synlett 2005, 2747 ; and references cited therein

<A NAME="RU02006ST-1D">1d</A> Grimmett MR. Comprehensive Heterocyclic Chemistry II Vol. 3: Katritzky AR. Rees CW. Scriven EFV. Elsevier Science; Oxford: 1996. p.77-220

<A NAME="RU02006ST-1E">1e</A> Ishihara M. Togo H. Synlett 2006, 227 ; and references cited therein

<A NAME="RU02006ST-2A">2a</A> Seijas JA. Vázquez-Tato MP. Martínez MM. Pizzolatti MG. Tetrahedron Lett. 2005, 46: 5827

<A NAME="RU02006ST-2B">2b</A> Lee Y. Lee J. Kim M. Kim T. Park H. Jew S. Org. Lett. 2005, 7: 1557

<A NAME="RU02006ST-2C">2c</A> Lee Y. Lee J. Kim M. Jeong B. Lee J. Kim T. Lee J. Ku J. Jew S. Park H. Org. Lett. 2005, 7: 3207

<A NAME="RU02006ST-2D">2d</A> Yang D. Yip Y. Wang X. Tetrahedron Lett. 1997, 38: 7083

<A NAME="RU02006ST-2E">2e</A> Hatano M. Asai T. Ishihara K. Chem. Lett. 2006, 35: 172

<A NAME="RU02006ST-3A">3a</A> Bhor S. Anilkumar G. Tse MK. Klawonn M. Dobler C. Bitterlich B. Grotevendt A. Beller M. Org. Lett. 2005, 7: 3393

<A NAME="RU02006ST-3B">3b</A> Langlois Y. Dalko PI. J. Org. Chem. 1998, 63: 8107

<A NAME="RU02006ST-3C">3c</A> Jones RCF. Nichols JR. Tetrahedron Lett. 1990, 31: 1771

<A NAME="RU02006ST-4A">4a</A> Nishiyama H. Sakaguchi H. Nakamura T. Horihata M. Kondo M. Ito K. Organometallics 1989, 8: 846

<A NAME="RU02006ST-4B">4b</A> Nishiyama H. Park S.-B. Itoh K. Tetrahedron: Asymmetry 1992, 3: 1029

<A NAME="RU02006ST-4C">4c</A> Lu J. Ji S. Teo Y. Loh T. Tetrahedron Lett. 2005, 46: 7435

<A NAME="RU02006ST-4D">4d</A> Ono F. Kanemasa S. Tanaka J. Tetrahedron Lett. 2005, 46: 7623

<A NAME="RU02006ST-4E">4e</A> Zhao C. Duffy MO. Taylor SJ. Morken JP. Org. Lett. 2001, 3: 1829

<A NAME="RU02006ST-4F">4f</A> Lee J. Miller JJ. Hamilton SS. Sigmann MS. Org. Lett. 2005, 7: 1837

<A NAME="RU02006ST-4G">4g</A> Sibi MP. Patil K. Org. Lett. 2005, 7: 1453

<A NAME="RU02006ST-4H">4h</A> Gissible A. Finn MG. Reiser O. Org. Lett. 2005, 7: 2325

<A NAME="RU02006ST-4I">4i</A> Menges F. Neuburger M. Pfaltz A. Org. Lett. 2002, 4: 4713

<A NAME="RU02006ST-4J">4j</A> Meiere SH. Valahovie MT. Harmann WD. J. Am. Chem. Soc. 2002, 124: 15099

<A NAME="RU02006ST-5A">5a</A> Heuser S. Keenan M. Weichert AG. Tetrahedron Lett. 2005, 46: 9001

<A NAME="RU02006ST-5B">5b</A> Chakraborty R. Franz V. Bez G. Vasadia D. Popuri C. Zhao C. Org. Lett. 2005, 7: 4145

<A NAME="RU02006ST-5C">5c</A> Weissberg A. Halak B. Portnoy M. J. Org. Chem. 2005, 70: 4556

<A NAME="RU02006ST-5D">5d</A> Sakakura A. Kondo R. Ishihara K. Org. Lett. 2005, 7: 1971

<A NAME="RU02006ST-5E">5e</A> Atkins JM. Vedejs E. Org. Lett. 2005, 7: 3351

<A NAME="RU02006ST-5F">5f</A> Yadav PP. Ahmad G. Maurya R. Tetrahedron Lett. 2005, 46: 5621

<A NAME="RU02006ST-5G">5g</A> Griffith JA. Rowlands GJ. Synthesis 2005, 3446

<A NAME="RU02006ST-5H">5h</A> Badiang JG. Aube J. J. Org. Chem. 1996, 61: 2484

<A NAME="RU02006ST-6A">6a</A> Gogoi P. Konwar D. Tetrahedron Lett. 2006, 47: 79

<A NAME="RU02006ST-6B">6b</A> Fujioka H. Murai K. Ohba Y. Hiramatsu A. Kita Y. Tetrahedron Lett. 2005, 46: 2197

<A NAME="RU02006ST-6C">6c</A> You S. Kelly JW. Org. Lett. 2004, 6: 1681

<A NAME="RU02006ST-6D">6d</A> Neef G. Eder U. Sauer G. J. Org. Chem. 1981, 46: 2824

<A NAME="RU02006ST-6E">6e</A> Anastassiadou M. Baziard-Mouysset G. Payard M. Synthesis 2000, 1814

<A NAME="RU02006ST-6F">6f</A> Peddibhotla S. Tepe JJ. Synthesis 2003, 1433

<A NAME="RU02006ST-6G">6g</A> Amemiya Y. Miller DD. Hsu F. Synth. Commun. 1990, 20: 2483

<A NAME="RU02006ST-6H">6h</A> Martin PK. Matthews HR. Rapoport H. Thyagarajan G. J. Org. Chem. 1968, 33: 3758

<A NAME="RU02006ST-7A">7a</A> Sayama S. Onami T. Synlett 2004, 2369

<A NAME="RU02006ST-7B">7b</A> Sayama S. Heterocycles 2005, 65: 1347

<A NAME="RU02006ST-8A">8a</A> Aoyama T. Takido T. Kodomari M. Tetrahedron Lett. 2005, 46: 1989

<A NAME="RU02006ST-8B">8b</A> Sayama S. Onami T. Synlett 2004, 2739

<A NAME="RU02006ST-9">9</A> Kavala V. Naik S. Patel BK. J. Org. Chem. 2005, 70: 4267

The reaction of ethylenediamine and aromatic dialdehydes such as terephthalaldehyde, isophthalaldehyde, and phthalaldehyde with PHPB took place to give no respective diimidazilines under the same reaction conditions.

It was assumed that steric hindrance between the formyl group and the methyl group exerted influence on the decrease in the yield of the corresponding oxazoline.

The products were complicated. The steric hindrance of two formyl groups in phthalaldehyde was supposed to inhibit generation of the respective dioxazoline.

The yields of nonanal (ca. 50%) and hydroxyimine (ca. 20%) were determined by ¹H NMR analysis of crude products.

Typical Procedure for Preparation of Imidazoline from Aldehyde.
To a solution of 4-bromobenzaldehyde (1, 46 mg, 0.25 mmol) in H₂O (6 mL) were added PHPB (160 mg, 0.5 mmol). Etylenediamine [90 mg (100 µL), 1.5 mmol] was added. After stirring for 15 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 and successively washed with 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 CHCl₃. Imidazoline 1a (50 mg, 0.22 mmol) was obtained in 88% yield.

Typical Procedure for Preparation of Oxazoline from Aldehyde.
To a solution of 4-bromobenzaldehyde (1, 46 mg, 0.25 mmol) in H₂O (6 mL) were added PHPB (240 mg, 0.75 mmol). 2-Aminoethanol [92 mg (90 µL), 1.5 mmol] was added. After stirring for 23 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 and successively washed with 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 CHCl₃. Oxazoline 1c (50 mg, 0.22 mmol) was obtained in 89% yield.