Ethyl 2-formylcyclopropanecarboxylate → HCID 57554524、化合物

HRID 551968

反応式

HRID 551968 の反応式
[CH2:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]#[C:12][C:13]2[CH:31]=[CH:30][C:16]([CH2:17][NH:18][C:19]3[CH:20]=[CH:21][C:22]([F:29])=[C:23]([CH:28]=3)[C:24]([O:26][CH3:27])=[O:25])=[CH:15][CH:14]=2)=[CH:7][CH:6]=1)[CH2:2][CH2:3][CH3:4].[CH2:32]([O:34][C:35]([CH:37]1[CH2:39][CH:38]1[CH:40]=O)=[O:36])[CH3:33].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.C([O-])(O)=O.[Na+]>ClCCCl>[CH2:1]([C:5]1[CH:6]=[CH:7][C:8]([C:11]#[C:12][C:13]2[CH:14]=[CH:15][C:16]([CH2:17][N:18]([CH2:40][CH:38]3[CH2:39][CH:37]3[C:35]([O:34][CH2:32][CH3:33])=[O:36])[C:19]3[CH:20]=[CH:21][C:22]([F:29])=[C:23]([CH:28]=3)[C:24]([O:26][CH3:27])=[O:25])=[CH:30][CH:31]=2)=[CH:9][CH:10]=1)[CH2:2][CH2:3][CH3:4]

参加物

6

反応物 4

HCID 89334Ethyl 2-formylcyclopropanecarboxylateHCID 516892Sodium BicarbonateHCID 2724942TriacetoxyborohydrideHCID 11452740Methyl 5-({4-[(4-butylphenyl)ethynyl]benzyl}amino)-2-fluorobenzoate

生成物 1

HCID 57554524HCID 57554524、化合物収率 65%

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒

反応条件

温度
50 °C

実験手順

To solution of methyl 5-({4-[(4-butylphenyl)ethynyl]benzyl}amino)-2-fluorobenzoate (500 mg; 1.20 mmol) in anhydrous DCE (30 mL) were added ethyl-2-formyl-1-cyclopropanecarboxylate (Aldrich, 0.40 mL; 3.01 mmol), triacetoxyborohydride (382 mg; 1.81 mmol).The resulting mixture was stirred at 50° C. under N2 atmosphere for 4 hours. The mixture was poured into a saturated solution of NaHCO3 (50 mL) and extracted with DCM (2×50 mL). The combined organic layers were washed with brine (100 mL), dried over magnesium sulfate, filtrated and the solvents were removed under reduced pressure to give 872 mg. Purification of this crude by flash chromatography on silicagel (c-Hex/EtOAc, gradient 95:5 to 90:10) gave 340 mg (65%) of the title compound as a yellow oil. HPLC, Rt: 6.06 min (purity=96.2%). LC/MS, M+(ESI): 542.3. 1H NMR (CDCl3) δ: 7.43 (t, J=8.5 Hz, 4H), 7.32 (m, 1H), 7.22 (d, J=7.9 Hz, 2H), 7.15 (d, J=7.9 Hz, 2H), 6.93 (m, 2H), 4.54 (s, 2H), 4.08 (m, 2H), 3.89 (s, 3H), 3.35 (m, 2H), 2.61 (t, J=7.5 Hz, 2H), 1.32-1.58 (m, 7H), 1.24 (t, J=7.0 Hz, 3H), 0.92 (t, J=7.3 Hz, 3H), 0.88 (m, 1H).

後処理

  1. customresulting mixture
  2. extractionextracted with DCM (2×50 mL)
  3. washThe combined organic layers were washed with brine (100 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltrated
  6. customthe solvents were removed under reduced pressure
  7. customto give 872 mg
  8. customPurification of this crude by flash chromatography on silicagel (c-Hex/EtOAc, gradient 95:5 to 90:10)

出典と根拠

ORDレコード
ord-7edda0d8f6b84f76a63ee1578a022afe
出典データセット
uspto-grants-2011_05
特許番号
US07947851B2

関連ノート

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