Triethylamine → 2-Acryloyl-6-(methyloxy)-7-nitro-1,2,3,4-tetrahydroisoquinoline

HRID 1014354ノート

反応式

HRID 1014354 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[N+:13]([O-:15])=[O:14])[CH2:9][NH:8][CH2:7][CH2:6]2.[C:16](Cl)(=[O:19])[CH:17]=[CH2:18].C(N(CC)CC)C>ClCCl.CN(C)C1C=CN=CC=1.O>[C:16]([N:8]1[CH2:7][CH2:6][C:5]2[C:10](=[CH:11][C:12]([N+:13]([O-:15])=[O:14])=[C:3]([O:2][CH3:1])[CH:4]=2)[CH2:9]1)(=[O:19])[CH:17]=[CH2:18]

参加物

7

反応物 3

HCID 8471TriethylamineHCID 13140Acryloyl chlorideHCID 594418746-Methoxy-7-nitro-1,2,3,4-tetrahydroisoquinoline

生成物 1

HCID 594417802-Acryloyl-6-(methyloxy)-7-nitro-1,2,3,4-tetrahydroisoquinoline収率 84.2%

試薬・触媒・溶媒 3

HCID 142844-(Dimethylamino)pyridine触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

A solution of 6-(methyloxy)-7-nitro-1,2,3,4-tetrahydroisoquinoline (1.6 g, 7.7 mmol) in dichloromethane (30 mL) was treated with acryloyl chloride (1.9 mL, 23 mmol, TCl), triethylamine (3.2 mL, 23 mmol, Aldrich), and catalytic 4-dimethylaminopyridine (50 mg 0.41 mmol, Aldrich). The mixture was stirred for 16 h, diluted with excess water, and extracted with ethyl acetate. The organic layer was separated, dried over magnesium sulfate, filtered, and concentrated to provide 2-acryloyl-6-(methyloxy)-7-nitro-1,2,3,4-tetrahydroisoquinoline (1.7 g, 84%). 1H NMR (400 MHz, DMSO-d6) is complicated due to amide rotomers δ ppm 2.86-2.95 (two triplets at 2.88 and 2.93, 2 H), 3.72-3.82 (two triplets at 3.74 and 3.80, 2 H), 3.89 (m, 3 H), 4.63-4.80 (two singlets at 4.65 and 4.77, 2 H), 5.73 (app d, J=10.3 Hz, 1 H), 6.16 (dd, J=16.7, 2.4 Hz, 1 H), 6.89 (dd, J=16.9, 10.3 Hz, 1 H), 7.21 (s, 1 H), 7.78-7.84 (two singlets at 7.79 and 7.83, 1 H); ESIMS (M+H)+=263.

後処理

  1. extractionextracted with ethyl acetate
  2. customThe organic layer was separated
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-8cc9bedb7beb4f339b8310f7a67bc626
出典データセット
uspto-grants-2011_07
特許番号
US07981903B2

反応ノート

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