An Efficient Preparation of 2-Imidazolines and Imidazoles from Aldehydes with Molecular Iodine and (Diacetoxyiodo)benzene

Midori Ishihara; Hideo Togo

doi:10.1055/s-2005-923604

LETTER

An Efficient Preparation of 2-Imidazolines and Imidazoles from Aldehydes with Molecular Iodine and (Diacetoxyiodo)benzene

Midori Ishihara^a, Hideo Togo*^a,b
^a Graduate School of Science and Technology, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
^b Faculty of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
e-Mail: togo@faculty.chiba-u.jp;

Abstract

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Abstract

2-Imidazolines were easily prepared in quite good yields from the reaction of aldehydes and ethylenediamine with molecular iodine in the presence of potassium carbonate. Moreover, 2-imidazolines obtained were smoothly oxidized to the corresponding imidazoles in good yields using (diacetoxyiodo)benzene at room temperature.

Key words

2-imidazoline - imidazole - iodine - (diacetoxyiodo)benzene - aldehyde - ethylenediamine

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References and Notes

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Typical Procedure for Preparation of 2-Imidazolines from Aldehydes: To a solution of p-tolualdehyde (120.2 mg, 1 mmol) in t-BuOH (10 mL) was added ethylenediamine (66.1 mg, 1.1 mmol). The obtained mixture was stirred at r.t. under an argon atmosphere for 30 min, and then K₂CO₃ (414.6 mg, 3 mmol) and I₂ (317.3 mg, 1.25 mmol) were added to the mixture and stirred at 70 °C. After 3 h, the mixture was quenched with sat. aq Na₂SO₃ until the iodine color almost disappeared, and was extracted with CHCl₃. The organic layer was washed with sat. aq NaHCO₃ and brine, and dried over Na₂SO₄. After filtration, the mixture was evaporated in vacuo to provide 160.2 mg of 2-(4-methylphenyl)imidazoline in 100% yield in an almost-pure state. Mp 181-182 °C (lit. [11] mp 181 °C). IR (KBr): 3140, 2925, 1600, 1495, 985, 830 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.38 (s, 3 H), 3.77 (s, 4 H), 7.21 (d, J = 8.3 Hz, 2 H), 7.67 (d, J = 8.3 Hz, 2 H).

Typical Procedure for Oxidation of 2-Imidazolines to Imidazoles: To a mixture of 2-(4-methylphenyl)imidazoline (160.2 mg, 1 mmol) and K₂CO₃ (152.0 mg, 1.1 mmol) in DMSO (10 mL) was added DIB (354.3 mg, 1.1 mmol). Then the mixture was stirred for 24 h at r.t. under an argon atmosphere. After the reaction, the reaction mixture was diluted with sat. aq NaHCO₃ and EtOAc, and was stirred for 5 min. The mixture was extracted with EtOAc and the organic layer was dried over Na₂SO₄. After filtration, the mixture was evaporated in vacuo. The residue was chromatographed on neutral silica gel (EtOAc-MeOH, 30:1) to give 128.1 mg of 2-(4-methylphenyl)imidazole in 81% yield in an almost-pure state. Mp 217-218 °C (lit. [5d] mp 218-220 °C). IR (KBr): 3460, 1515, 1445, 1100, 820, 730 cm^-1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 2.31 (s, 3 H), 6.97 (br s, 1 H), 7.19 (br s, 1 H), 7.21 (d, J = 8.2 Hz, 2 H), 7.81 (d, J = 8.2 Hz, 2 H), 12.38 (s, 1 H).

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