Synlett 2014; 25(3): 423-427
DOI: 10.1055/s-0033-1340300
letter
© Georg Thieme Verlag Stuttgart · New York

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

Nelson A. M. Pereira
a  Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal   Email: [email protected]
,
Susana M. M. Lopes
a  Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal   Email: [email protected]
,
Américo Lemos*
b  CIQA, FCT, University of Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
,
Teresa M. V. D. Pinho e Melo*
a  Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 17 September 2013

Accepted after revision: 28 October 2013

Publication Date:
04 December 2013 (online)


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.

Supporting Information

 
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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): νmax = 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): νmax = 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.