Dimethylformamide → HCID 66749408, compound

HRID 2402167Notes

Reaction equation

HRID 2402167 reaction equation
[Br:1][C:2]1[CH:6]=[C:5]([N:7]2[CH2:12][CH2:11][O:10][CH2:9][CH2:8]2)[S:4][C:3]=1[C:13]([O:15][CH2:16][CH3:17])=[O:14].CN(C=O)C.[Br:23]N1C(=O)CCC1=O.CCOC(C)=O>CCCCCC>[Br:1][C:2]1[C:6]([Br:23])=[C:5]([N:7]2[CH2:12][CH2:11][O:10][CH2:9][CH2:8]2)[S:4][C:3]=1[C:13]([O:15][CH2:16][CH3:17])=[O:14]

Participants

6

Reactant 4

HCID 6228Dimethylformamide2×HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 66749818HCID 66749818, compound

Product 1

HCID 66749408HCID 66749408, compoundYield 69.1%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

To a degassed solution of ethyl 3-bromo-5-morpholin-4-ylthiophene-2-carboxylate (0.688 g, 2.15 mmol) in DMF (14 mL, 180 mmol) was added N-bromosuccinimide (0.7648 g, 4.297 mmol) dropwise as a solution in degassed DMF (4.1 mL, 52 mmol). The mixture was wrapped in foil to protect from ambient light, and the reaction was stirred under argon at room temperature for 2 hours. The reaction mixture was quenched via addition of 10% sodium thiosulfate solution (10 mL) and then diluted with EtOAc (30 mL). The layers were separated, and the aqueous layer was extracted with EtOAc (10 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo. Flash chromatography (eluent: 0-25% EtOAc:hexane) afforded ethyl 3,4-dibromo-5-(morpholin-4-yl)thiophene-2-carboxylate (593 mg, yield 69%). LCMS: (FA) ES+ 398, 400, 402; 1H NMR (400 MHz, DMSO) δ 4.26 (q, J=7.1 Hz, 2H), 3.75 (dd, J=5.5, 3.8 Hz, 4H), 3.24-3.10 (m, 4H), 1.27 (t, J=7.1 Hz, 3H).

Workup

  1. customThe reaction mixture was quenched via addition of 10% sodium thiosulfate solution (10 mL)
  2. additiondiluted with EtOAc (30 mL)
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with EtOAc (10 mL)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8a6359a33ab545ab9a9c02c12d7748b0
Source dataset
uspto-grants-2014_08
Patent number
US08796271B2

Reaction notes

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