Oxalyl chloride → 9-bromo-N-(2,4-dichlorophenyl)-N-methyl-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxamide

HRID 2079008Notes

Reaction equation

HRID 2079008 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][C:11]3[CH:10]=[C:9]([C:15]([OH:17])=O)[S:8][C:7]=3[C:6]=2[CH:18]=1.C(Cl)(=O)C(Cl)=O.C(=O)([O-])O.[Na+].[Cl:30][C:31]1[CH:38]=[C:37]([Cl:39])[CH:36]=[CH:35][C:32]=1[NH:33][CH3:34]>ClCCl.CN(C=O)C.C(#N)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][C:11]3[CH:10]=[C:9]([C:15]([N:33]([C:32]4[CH:35]=[CH:36][C:37]([Cl:39])=[CH:38][C:31]=4[Cl:30])[CH3:34])=[O:17])[S:8][C:7]=3[C:6]=2[CH:18]=1

Participants

9

Reactant 4

HCID 65578Oxalyl chlorideHCID 516892Sodium BicarbonateHCID 28009352,4-Dichloro-N-methylanilineHCID 668685729-Bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azulene-2-carboxylic acid

Product 1

HCID 579004939-bromo-N-(2,4-dichlorophenyl)-N-methyl-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxamide

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 9-bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azulene-2-carboxylic acid (911 mg) in dichloromethane (20 mL) and DMF (1 drop) was added oxalyl chloride (0.42 mL) and the reaction stirred at room temperature for 3 h. The solvent was then reduced in vacuo and the residue redissolved in acetonitrile. Sodium hydrogen carbonate (259 mg) and 2,4-dichloro-N-methylaniline (546 mg) were added and the reaction stirred at room temperature for 16 h. Water (20 mL) was added and the product extracted into ethyl acetate (2×20 mL). The organics were dried (MgSO4), reduced in vacuo and purified on silica to give 356. NMR: (CDCl3): 2.95-2.98 (2H, m), 3.29 (3H, s, Me), 4.13-4.16 (2H, m), 6.72 (1H, s, Ar), 6.78 (1H, d, J 8.6, Ar), 7.16 (1H, dd, J 8.6 and 2.3, Ar), 7.22 (1H, d, J 8.5, Ar), 7.29 (1H, dd, J 8.4 and 2.2, Ar) and 7.48-7.52 (1H, m, Ar)

Workup

  1. stirringthe reaction stirred at room temperature for 16 h
  2. extractionthe product extracted into ethyl acetate (2×20 mL)
  3. dry with materialThe organics were dried (MgSO4)
  4. custompurified on silica

Sources & evidence

ORD record
ord-c3e27ee7e9b344f9af41b252e727b20a
Source dataset
uspto-grants-2011_04
Patent number
US07928248B2

Reaction notes

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