Synlett 2016; 27(09): 1413-1417
DOI: 10.1055/s-0035-1561571
letter
© Georg Thieme Verlag Stuttgart · New York

An Efficient Protocol for Formylation of Amines Using Carbon Dioxide and PMHS under Transition-Metal-Free Conditions

Deepak B. Nale
Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400019, India   Email: bm.bhanage@gmail.com   Email: bm.bhanage@ictmumbai.edu.in
,
Bhalchandra M. Bhanage*
Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400019, India   Email: bm.bhanage@gmail.com   Email: bm.bhanage@ictmumbai.edu.in
› Author Affiliations
Further Information

Publication History

Received: 28 November 2015

Accepted after revision: 17 January 2016

Publication Date:
18 February 2016 (eFirst)

Abstract

A highly efficient, green and simple base catalytic system was investigated for the formylation of amines using CO2 and PMHS [poly(methylhydrosiloxane)] under mild reaction conditions. This reaction proceeds smoothly without additives and furnishes the corresponding N-formylated products from both the 1° and the 2° aliphatic as well as aromatic amines in good to excellent yields.

Supporting Information

 
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  • 20 General Procedure for the Synthesis of Formamide Derivatives: The catalyst (10.0 mol%) was introduced into a 100-mL autoclave equipped with an overhead stirrer and an automatic temperature control system5i containing amine (1 mmol), PMHS (4.0 mmol) and THF (5.0 mL) at r.t. After sealing and flushing the reactor three times with 10 atm of N2, followed by the CO2 to the desired pressure, the reactor was heated and stirred vigorously at 530–600 rpm for 12 h. After completion of the reaction, the reactor was cooled to r.t. and the pressure was carefully released. Basic hydrolysis of the reaction mixture was carried out as previously described.5h The reaction mixture was then extracted with EtOAc (3 × 10 mL), the combined organic layers were dried over anhyd Na2SO4, filtered and evaporated in vacuo. The isolated crude oil product was further purified by column chromatography on 100–200 mesh size silica gel (elution with 20:4 → 10:2 petroleum ether–EtOAc) to provide the corresponding pure compound. The spectroscopic data are consistent with those reported in the literature and in agreement with the assigned structures.21 Morpholine-4-carbaldehyde (2a): colorless oil; yield: 99%. 1H NMR (400 MHz, 30 °C, CDCl3, TMS): δ = 7.92 (s, 1 H), 3.58–3.52 (m, 4 H), 3.44 (t, J = 4.0 Hz, 2 H), 3.28 (t, J = 4.0 Hz, 2 H). 13C NMR (100 MHz, 30 °C, CDCl3, TMS): δ = 160.81, 67.08, 66.26, 45.67, 40.44. GC–MS (EI): m/z (%) = 115 (100) [M]+. Indoline-1-carbaldehyde (2o): brown solid; yield: 78%. 1H NMR (400 MHz, 30 °C, CDCl3, TMS): δ (mixture of rotamers) = 8.92 (s, 1 H, major), 8.50 (s, 1 H, minor), 7.24–7.14 (m, 3 H), 7.05–7.01 (m, 1 H), 4.05 (t, J = 8.0 Hz, 2 H), 3.14 (t, J = 8.0 Hz, 2 H). 13C NMR (100 MHz, 30 °C, CDCl3, TMS): δ = 157.58, 140.93, 127.57, 126.06, 125.13, 124.28, 109.38, 44.64, 27.17. GC–MS (EI): m/z (%) = 147 (65) [M]+. N-Benzyl-N-methylformamide (2q): colorless oil; yield: 95%. 1H NMR (400 MHz, CDCl3, 30 °C, TMS): δ (mixture of rotamers) = 8.26 (s, 1 H, major), 8.13 (s, 1 H, minor), 7.37–7.17 (m, 5 H), 4.50 (s, 2 H, minor), 4.37 (s, 2 H, major), 2.82 (s, 3 H, minor), 2.76 (s, 3 H, major). 13C NMR (100 MHz, 30 °C, CDCl3, TMS): δ (mixture of rotamers) = 162.74 (major), 162.57 (minor), 135.96 (minor), 135.69 (major), 128.88 (major), 128.67 (minor), 128.21 (major), 128.08 (minor), 127.62 (minor), 127.36 (major), 53.47 (major), 47.74 (minor), 34.05 (major), 29.44 (minor). GC–MS (EI): m/z (%) = 149 (100) [M]+. N-Methyl-N-phenylformamide (2s): brownish oil; yield: 93%. 1H NMR (400 MHz, 30 °C, CDCl3, TMS): δ = 8.39 (s, 1 H), 7.33 (t, J = 8.0 Hz, 2 H), 7.20 (t, J = 8.0 Hz, 1 H), 7.10 (d, J = 4.0 Hz, 2 H), 3.24 (s, 3 H). 13C NMR (100 MHz, CDCl3, 30 °C, TMS): δ (mixture of rotamers) = 162.27 (major), 162.17 (minor), 142.08, 129.55, 128.96, 126.32 (major), 126.16 (minor), 123.53, 122.26, 31.95. GC–MS (EI): m/z (%) = 135 (85) [M]+.
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