5-(2-Nitroethenyl)-1,3-benzodioxole → Methyl 2-(4-hexenoyl)-4-nitro-3-(1,3-benzodioxole-5-yl)butyrate

HRID 3003

反応式

HRID 3003 の反応式
[O:1]=[C:2]([CH2:8][CH2:9][CH:10]=[CH:11][CH3:12])[CH2:3][C:4]([O:6][CH3:7])=[O:5].[N+:13]([CH:16]=[CH:17][C:18]1[CH:26]=[CH:25][C:21]2[O:22][CH2:23][O:24][C:20]=2[CH:19]=1)([O-:15])=[O:14].C(OCC)(=O)C.CCCCCC>C(O)(C)C.C1COCC1.C1CCN2C(=NCCC2)CC1>[C:2]([CH:3]([CH:17]([C:18]1[CH:26]=[CH:25][C:21]2[O:22][CH2:23][O:24][C:20]=2[CH:19]=1)[CH2:16][N+:13]([O-:15])=[O:14])[C:4]([O:6][CH3:7])=[O:5])(=[O:1])[CH2:8][CH2:9][CH:10]=[CH:11][CH3:12]

参加物

7

反応物 3

HCID 949455-(2-Nitroethenyl)-1,3-benzodioxoleHCID 51284636-Octenoic acid,3-oxo-, methyl esterHCID 21226206Ethyl acetate hexane

生成物 1

HCID 53959667Methyl 2-(4-hexenoyl)-4-nitro-3-(1,3-benzodioxole-5-yl)butyrate収率 82%

試薬・触媒・溶媒 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene触媒HCID 3776Isopropanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of methyl 3-oxo-6-octenoate (502 mg, 2.95 mmol) in 10 mL of isopropanol was added to a solution of 5-(2-nitrovinyl)-1,3-benzodioxole (712 mg, 3.69 mmol) in 10 mL THF, then DBU (22 μL, 0.15 mmol) was added. The resulting reddish solution was stirred at room temperature for 20 minutes. TLC (ethyl acetate-hexane, 1:3) indicated complete consumption of ketoester. The solution was concentrated in vacuo and flash chromatographed on silica gel eluting with 18% ethyl acetate in hexane to produce 879 mg (2.42 mmol, 82%) of the title compound as a mixture of diastereomers in a 1:1 ratio. 1H NMR (CDCl3, 300 MHz) δ 1.55-1.66 (m, 3H), 2.02-2.17 (br m, 1H), 2.20-2.37 (m, 1.5H), 2.49-2.76 (m, 1.5H), 3.57 (s, 1.5H), 3.74 (s, 1.5H), 3.97 (d, J=7.5H, 0.5H), and 4.05 (d, J=8 Hz, 0.5H), 4.10-4.20 (m, 1H), 4.68-4.82 (m, 2H), 5.06-5.52 (m, 2H), 5.95 (2s, 2H), 6.65 (m, 1H), 6.68 (br s, 1H), 6.75 (d, 7.5 Hz, 1H). MS (DCl/NH3) m/e 381 (M+NH4)+. Anal calcd for C18H21NO7 : C, 59.50; H, 5.82; N, 3.85. Found: C, 59.32; H, 5.71; N, 3.72.

後処理

  1. customconsumption of ketoester
  2. concentrationThe solution was concentrated in vacuo and flash
  3. customchromatographed on silica gel eluting with 18% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-a43f21651da24fe980f402c4a2514be5
出典データセット
uspto-grants-1998_03
特許番号
US05731434

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