N-Methylbenzylamine → 3-(N-benzyl-N-methylaminomethyl)-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-2-(4-nitrophenyl)-4-oxothieno[2,3-b]pyridine

HRID 2304881Notes

Reaction equation

HRID 2304881 reaction equation
Br[CH2:2][C:3]1[C:11]2[C:10](=[O:12])[C:9]([C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])=[CH:8][N:7]([CH2:18][C:19]3[C:24]([F:25])=[CH:23][CH:22]=[CH:21][C:20]=3[F:26])[C:6]=2[S:5][C:4]=1[C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1.C(N(C(C)C)C(C)C)C.[CH3:45][NH:46][CH2:47][C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1.C(=O)([O-])[O-].[K+].[K+]>O.C(OC(C)C)(C)C.CN(C)C=O>[CH2:47]([N:46]([CH2:2][C:3]1[C:11]2[C:10](=[O:12])[C:9]([C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])=[CH:8][N:7]([CH2:18][C:19]3[C:24]([F:25])=[CH:23][CH:22]=[CH:21][C:20]=3[F:26])[C:6]=2[S:5][C:4]=1[C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1)[CH3:45])[C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1

Participants

8

Reactant 4

HCID 7669N-MethylbenzylamineHCID 11430Potassium CarbonateHCID 81531DiisopropylethylamineHCID 155504633-Bromomethyl-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-2-(4-nitrophenyl)-4-oxothieno[2,3-b]pyridine

Product 1

HCID 155504643-(N-benzyl-N-methylaminomethyl)-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-2-(4-nitrophenyl)-4-oxothieno[2,3-b]pyridineYield 97.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 7914Diisopropyl EtherSolvent

Conditions

Temperature
35 °C

Procedure

3-bromomethyl-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-2-(4-nitrophenyl)-4-oxothieno[2,3-b]pyridine (32 g), N,N-dimethylformamide (64 ml) and N-ethyldiisopropylamine (8.84 g) were mixed and treated dropwise with N-methylbenzylamine (8.29 g) with cooling on ice, and the reaction mixture was stirred at 30 to 40° C. for 5 hours. The reaction mixture was poured into a mixture of a solution of potassium carbonate (9.5 g) in water (320 ml) and diisopropylether (320 ml) and the reaction mixture was stirred at room temperature for 2 hours and then with cooling on ice for 1 hour, and the crystal precipitated was recovered by a filtration, washed with water (600 ml) and diusopropylether (160 ml), dried in vacuo at 50° C. for 4 hours to obtain the title compound (33.58 g, 97.9%).

Workup

  1. temperaturewith cooling on ice
  2. stirringthe reaction mixture was stirred at room temperature for 2 hours
  3. temperaturewith cooling on ice for 1 hour
  4. customthe crystal precipitated
  5. filtrationwas recovered by a filtration
  6. washwashed with water (600 ml) and diusopropylether (160 ml)
  7. customdried in vacuo at 50° C. for 4 hours

Sources & evidence

ORD record
ord-fabbe346f30e40f1bfc3de0e1a21fa1c
Source dataset
uspto-grants-2002_08
Patent number
US06437132B2

Reaction notes

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