On-Water Synthesis of Dipyrromethanes via Bis-Hetero-Diels–Alder Reaction of Azo- and Nitrosoalkenes with Pyrrole

Abstract

An unprecedented one-pot approach to 5-substituted dipyrromethanes based on the hetero-Diels–Alder reaction of azo- and nitrosoalkenes is described. The on-water reaction conditions led to the target compounds in higher yields with significantly shorter reaction times and simpler purification procedures than ­carrying out the reaction in dichloromethane or in the absence of solvent.

Key words

dipyrromethane - Diels–Alder reactions - on-water reactions - azoalkenes - nitrosoalkenes

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• 22 General Procedure for the Synthesis of Dipyrromethanes Hydrazone 1 (0.83 mmol) or oxime 4 was added to a solution of Na₂CO₃ (8.30 mmol) in H₂O (11 mL) and pyrrole (16.6 mmol). The reaction mixture was stirred at r.t. for 4 h. After this time the mixture was extracted with CH₂Cl₂ (3 × 20 mL) and dried over Na₂SO₄. After filtration, the solvent and the excess pyrrole were removed under reduced pressure. The product was crystallized with Et₂O–n-hexane, filtered, washed with hexane and dried under vacuum. 5-(1′-tert-Butoxycarbonylhydrazonoethyl)-dipyrromethane (2a) Yield: 82%; mp 137–138 °C (Et₂O–n-hexane). IR (KBr): ν_max = 3337, 2979, 1720, 1529, 1369, 1245, 1164, 715 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.74 (br s, 2 H, NH), 7.51 (s, 1 H, NH), 6.70 (br s, 2 H, α-H pyrrolic), 6.13 (br s, 2 H, β-H pyrrolic), 6.05 (br s, 2 H, β-H pyrrolic), 5.05 (s, 1 H, meso), 1.83 (s, 3 H, Me), 1.53 (s, 9 H, t-Bu) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 156.0, 152.9, 129.1, 117.6, 108.3, 106.9, 81.4, 46.4, 28.3, 13.9 ppm. ESI-HRMS: m/z calcd for C₁₆H₂₃N₄O₂ [M + H]⁺: 303.1815; found: 303.1813. (E)-5-(1′-Hydroxyiminoethyl)dipyrromethane (5a) Yield 74%; mp 142–144 °C (Et₂O–n-hexane). IR (KBr): ν_max = 3338, 1403, 1218, 1095, 1029, 948, 728 cm^–1. ¹H NMR (400 MHz, CDCl₃/DMSO-d ₆): δ = 10.02 (s, 1 H, OH), 9.37 (s, 2 H, NH), 6.67 (br s, 2 H, α-H pyrrolic), 6.06 (br s, 2 H, β-H pyrrolic), 5.97 (br s, 2 H, β-H pyrrolic), 5.00 (s, 1 H, meso), 1.84 (s, 9 H, Me) ppm. ¹³C NMR (100 MHz, CDCl₃/ DMSO-d ₆): δ = 157.0, 129.5, 117.2, 107.6, 106.5, 44.3, 12.3 ppm. ESI-HRMS: m/z calcd for C₁₁H₁₄N₃O [M + H]⁺: 204.1131; found: 204.1132.