Nitromethane → 1-Cyano-2-(1-ethyl-propyl)-cyclopropanecarboxylic acid benzyl ester

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Reaktionsgleichung

[CH2:1]([O:8][C:9](=[O:19])[C:10]([C:17]#[N:18])=[CH:11][CH:12]([CH2:15][CH3:16])[CH2:13][CH3:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+]([CH3:23])([O-])=O.C1CCN2C(=NCCC2)CC1>C(#N)C>[CH2:1]([O:8][C:9]([C:10]1([C:17]#[N:18])[CH2:23][CH:11]1[CH:12]([CH2:13][CH3:14])[CH2:15][CH3:16])=[O:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

Reaktionsbedingungen

Temperatur: 60 °C

Versuchsvorschrift

To a solution of 2-cyano-4-ethyl-hex-2-enoic acid benzyl ester (3.76 g, 14.6 mmol) in 80 mL acetonitrile was added nitromethane (3.95 mL, 73 mmol), followed by DBU (2.18 mL, 14.6 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 2.63 g (66%) of 1-cyano-2-(1-ethyl-propyl)-cyclopropanecarboxylic acid benzyl ester as a pale yellow oil. 1H NMR (CDCl3) δ 7.35 (m, 5H), 5.22 (m, 2H), 1.86 (dd, J=9.0, 4.6 Hz, 1H), 1.72 (m, 1H), 1.45–1.57 (m, 4H), 1.42 (dd, J=8.3, 4.6 Hz, 1H), 1.14 (m, 1H), 0.93 (m, 6H). 13C NMR δ 168.21, 135.12, 128.88, 128.73, 128.16, 117.77, 68.25, 42.41, 36.72, 26.18, 25.97, 25.20, 19.33, 11.19, 10.84. LRMS: m/z 272.1 (M+1). IR (neat) 2245, 1734 cm−1. Anal. Calcd for C17H21NO2: C, 75.25; H, 7.80; N, 5.16. Found: C, 75.44; H, 7.83; N, 5.22.

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag: ord-ae1c7b9473dd4141a5277e01ad5a0b5b
Quelldatensatz: uspto-grants-2006_04
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US07030267B2

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