Nitromethane → Ethyl 1-cyano-2-(2-methylpropyl)cyclopropanecarboxylate

HRID 1796820Notes

Reaction equation

[CH2:1]([O:3][C:4](=[O:13])[C:5]([C:11]#[N:12])=[CH:6][CH2:7][CH:8]([CH3:10])[CH3:9])[CH3:2].[N+]([CH3:17])([O-])=O.C1CCN2C(=NCCC2)CC1>C(#N)C>[CH2:1]([O:3][C:4]([C:5]1([C:11]#[N:12])[CH2:17][CH:6]1[CH2:7][CH:8]([CH3:10])[CH3:9])=[O:13])[CH3:2]

Participants

Conditions

Temperature: 60 °C

Procedure

To a solution of 2-cyano-5-methyl-hex-2-enoic acid ethyl ester (0.74 g, 4.08 mmol) in 16 mL acetonitrile was added nitromethane (1.11 mL, 20.4 mmol), followed by DBU (0.61 mL, 4.08 mmol) resulting in an orange solution. The reaction was heated to 60° C. for 16 hours, then cooled and partitioned between Et2O and 1N HCl (aq). The phases were separated, and the organic phase washed with brine, dried (MgSO4), and concentrated. Flash chromatography of the residue (5→10% EtOAc/hexanes) afforded 0.56 g (70%) of 1-cyano-2-isobutyl-cyclopropanecarboxylic acid ethyl ester as a pale yellow oil. 1H NMR (CDCl3) δ 4.22 (m, 2H), 1.75–1.90 (m, 3H), 1.63 (m, 1H), 1.36 (m, 2H), 1.30 (t, J=7.3 Hz, 3H), 0.95 (m, 6H). 13C NMR δ 168.25, 117.72, 62.94, 39.12, 30.25, 28.12, 25.66, 22.63, 22.40, 19.56, 14.30. LRMS: m/z 196.0 (M+1). Anal. Calcd for C11H17NO2: C, 67.66; H, 8.78; N, 7.17. Found: C, 67.32; H, 8.74; N, 7.32.

Workup

customresulting in an orange solution
temperaturecooled
custompartitioned between Et2O and 1N HCl (aq)
customThe phases were separated
washthe organic phase washed with brine
dry with materialdried (MgSO4)
concentrationconcentrated

Sources & evidence

ORD record: ord-4ef7d4e583314d02a73e3e4be0bd5051
Source dataset: uspto-grants-2006_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07030267B2

Reaction notes

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