Water → 7-(2-cyclopropylethynyl)-3,4-dihydro-2H-1-benzopyran-4-one

HRID 1525741ノート

反応式

HRID 1525741 の反応式
Br[C:2]1[CH:11]=[C:10]2[C:5]([C:6](=[O:12])[CH2:7][CH2:8][O:9]2)=[CH:4][CH:3]=1.C(N(CC)CC)C.[CH:20]1([C:23]#[CH:24])[CH2:22][CH2:21]1.O>CN(C=O)C.[Cu]I>[CH:20]1([C:23]#[C:24][C:2]2[CH:3]=[CH:4][C:5]3[C:6](=[O:12])[CH2:7][CH2:8][O:9][C:10]=3[CH:11]=2)[CH2:22][CH2:21]1

参加物

7

反応物 4

HCID 962WaterHCID 8471TriethylamineHCID 138823CyclopropylacetyleneHCID 223357367-bromo-3,4-dihydro-2H-1-benzopyran-4-one

生成物 1

HCID 867282157-(2-cyclopropylethynyl)-3,4-dihydro-2H-1-benzopyran-4-one収率 88.3%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

To a solution of 7-bromochroman-4-one (2.0 g, 8.8 mmol) in DMF (10 mL) was added CuI (380 mg, 1.7 mmol), Pd(PPh3)Cl2 (540 mg, 0.8 mmol) and triethylamine (5 mL) under nitrogen at rt. The suspension was warmed to 100° C. and then cyclopropylacetylene (1.1 g, 17.6 mmol) was added dropwise. The mixture was stirred at 100° C. under nitrogen for 2 h. The reaction mixture was cooled to rt, poured into water, and extracted with EtOAc. Organics were separated and washed with brine, dried (Na2SO4), and concentrated. The residue was purified by silica gel chromatography to give 1.65 g (88%) of the title compound as a tan solid. 1H NMR (300 MHz, CDCl3): δ 0.83-0.93 (4H, m), 1.44-1.49 (1H, m), 2.79 (2H, t, J=6.6 Hz), 4.52 (2H, t, J=6.6 Hz), 6.96-7.00 (2H, m), 7.79 (1H, d, J=7.8 Hz). [M+H] calc'd for C14H12O, 213; found 213.

後処理

  1. temperatureThe reaction mixture was cooled to rt
  2. extractionextracted with EtOAc
  3. customOrganics were separated
  4. washwashed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-ce86521ef6b447768eb1cb336e17df73
出典データセット
uspto-grants-2015_07
特許番号
US09085534B2

反応ノート

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