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

HRID 1796831ノート

反応式

HRID 1796831 の反応式
[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

参加物

5

反応物 3

HCID 6375NitromethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 695998522-Cyano-4-ethyl-hex-2-enoic acid benzyl ester

生成物 1

HCID 453578991-Cyano-2-(1-ethyl-propyl)-cyclopropanecarboxylic acid benzyl ester収率 66.4%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
60 °C

実験手順

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.

後処理

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

出典と根拠

ORDレコード
ord-ae1c7b9473dd4141a5277e01ad5a0b5b
出典データセット
uspto-grants-2006_04
特許番号
US07030267B2

反応ノート

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