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

HRID 1796831노트

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HRID 1796831 반응식
[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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 6342Acetonitrile용매

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온도
60 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-ae1c7b9473dd4141a5277e01ad5a0b5b
출처 데이터셋
uspto-grants-2006_04
특허 번호
US07030267B2

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