N,N'-Dimethylethylenediamine → methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate

HRID 1911024ノート

反応式

HRID 1911024 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][C:8]([C:12]([O:14][CH3:15])=[O:13])=[C:7]([CH3:16])[C:6]=2[CH:17]=1.FC(F)(F)C([NH2:22])=O.CNCCNC.C(=O)([O-])[O-].[K+].[K+]>O1CCOCC1.[Cu]I.CO.O>[NH2:22][C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][C:8]([C:12]([O:14][CH3:15])=[O:13])=[C:7]([CH3:16])[C:6]=2[CH:17]=1

参加物

9

反応物 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium Carbonate2 回HCID 67717TrifluoroacetamideHCID 71060937(E)-methyl 2-bromo-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate

生成物 1

HCID 86685426methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate収率 66%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 887Methanol溶媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
120 °C

実験手順

To a solution of (E)-methyl 2-bromo-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate from step B2 of preparation B (500 mg, 1.694 mmol) in dioxane (5 mL) was added 2,2,2-trifluoroacetamide (1.92 g, 16.94 mmol), copper(I) iodide (323 mg, 1.69 mmol), N1,N2-dimethylethane-1,2-diamine (448 mg, 5.08 mmol) and potassium carbonate (702 mg, 5.08 mmol). The mixture was heated in a microwave reactor at 120° C. for 2 h and 15 min. Then water (3 mL), MeOH (3 mL), and potassium carbonate (1 g) were added. The mixture was stirred at rt for 16 h. The mixture was concentrated, the residue was diluted with water (50 mL), and the mixture was extracted with EtOAc. The organic layers were combined, and concentrated. The residue was purified by silica gel column chromatography (hexanes-50% EtOAc) to afford methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate (260 mg, 1.12 mmol, 66% yield). 1H NMR (400 MHz, chloroform-d) δ 6.96 (d, J=8.0 Hz, 1H), 6.65 (d, J=2.3 Hz, 1H), 6.58 (dd, J=7.8, 2.5 Hz, 1H), 3.80 (s, 3H), 3.62 (br. s., 2H), 2.46 (t, J=6.9 Hz, 2H), 2.37 (s, 3H), 2.17-2.01 (m, 4H).

後処理

  1. concentrationThe mixture was concentrated
  2. additionthe residue was diluted with water (50 mL)
  3. extractionthe mixture was extracted with EtOAc
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel column chromatography (hexanes-50% EtOAc)

出典と根拠

ORDレコード
ord-4e155df29f4d4ed189361e6a335efe00
出典データセット
uspto-grants-2013_12
特許番号
US08604024B2

反応ノート

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