Acetonitrile → HCID 68777976, compound

HRID 2191088Notes

Reaction equation

HRID 2191088 reaction equation
N([O:3][C:4]([CH3:7])(C)C)=O.[NH2:8][C:9]1[S:10][C:11]2[C:19](=[O:20])[CH2:18][CH2:17][CH2:16][C:12]=2[C:13]=1[C:14]#[N:15].[C:21](#N)[CH3:22]>[Cu](Br)Br>[N:8]1([C:9]2[S:10][C:11]3[C:19](=[O:20])[CH2:18][CH2:17][CH2:16][C:12]=3[C:13]=2[C:14]#[N:15])[CH2:7][CH2:4][O:3][CH2:22][CH2:21]1

Participants

5

Reactant 3

HCID 6342AcetonitrileHCID 10906Tert-Butyl nitriteHCID 136673402-Amino-7-oxo-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile

Product 1

HCID 68777976HCID 68777976, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 24611Copper bromide (CuBr2)Catalyst

Procedure

Tert-butyl nitrite (4.6 mL, 4.3 mmol) was added to a cooled mixture of copper(II) bromide (10.5 g, 46.9 mmol) in acetonitrile (50 mL). 2-Amino-7-oxo-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile (6.0 g, 31.3 mmol) was then added over a period of 1 h and the reaction mixture was then allowed to warm to room temperature. The solvent was removed in vacuo and the residue was partitioned between DCM and 1M aqueous HCl. The organic phase was dried (magnesium sulfate) and concentrated in vacuo. The residue was purified by column chromatography (SiO2, 0-100% EtOAc/heptane) and the isolated product was combined with morpholine (4.5 mL) in DMSO (80 mL). The reaction mixture was heated at 100° C. for 1.5 h, then water (300 mL) was immediately added with rapid stirring and the mixture was allowed to cool to room temperature overnight. The precipitate was filtered off, washed with water and dried in vacuo to give the title compound (5.65 g, 69%) as a pale brown solid. δH (DMSO-d6) 3.80-3.72 (4H, m), 3.67-3.59 (4H, m), 2.73 (2H, t, J 6.0 Hz), 2.49-2.42 (2H, m), 2.13-2.03 (2H, m). LCMS (ES+) 263.2 (M+H)+.

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residue was partitioned between DCM and 1M aqueous HCl
  3. dry with materialThe organic phase was dried (magnesium sulfate)
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by column chromatography (SiO2, 0-100% EtOAc/heptane)
  6. temperatureThe reaction mixture was heated at 100° C. for 1.5 h
  7. additionwater (300 mL) was immediately added
  8. temperatureto cool to room temperature overnight
  9. filtrationThe precipitate was filtered off
  10. washwashed with water
  11. customdried in vacuo

Sources & evidence

ORD record
ord-74bbc7a0c9024c6d9120e76f700b9d1a
Source dataset
uspto-grants-2012_12
Patent number
US08324204B2

Reaction notes

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