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

HRID 1014354Notes

Reaction equation

HRID 1014354 reaction equation
[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]

Participants

7

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

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.

Workup

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

Sources & evidence

ORD record
ord-8cc9bedb7beb4f339b8310f7a67bc626
Source dataset
uspto-grants-2011_07
Patent number
US07981903B2

Reaction notes

Loading…