Ammonium Chloride → HCID 59733669, compound

HRID 132072Notes

Reaction equation

HRID 132072 reaction equation
C([Mg]Cl)(C)C.Br[C:7]1[CH:8]=[C:9]([C:13]#[N:14])[S:10][C:11]=1[Cl:12].C[O:16][S:17]([C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([Br:25])[CH:20]=1)=O.[Cl-].[NH4+]>C1COCC1.C(OCC)(=O)C>[Br:25][C:21]1[CH:20]=[C:19]([S:17]([C:7]2[CH:8]=[C:9]([C:13]#[N:14])[S:10][C:11]=2[Cl:12])=[O:16])[CH:24]=[CH:23][CH:22]=1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 597336483-Bromobenzenesulfinic acid methyl esterHCID 597336644-Bromo-5-chlorothiophene-2-carbonitrileHCID 178418918HCID 178418918, compound

Product 1

HCID 59733669HCID 59733669, compoundYield 85.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Isopropyl magnesium chloride solution (Aldrich, 2.0 M in THF, 2.92 mL, 5.84 mmol) was added dropwise over 1.5 hours to a −78° C. suspension of 4-bromo-5-chloro-thiophene-2-carbonitrile (Example 24: step b, 1 g, 4.49 mmol) in THF (anhydrous, 20 mL) under argon. The reaction mixture was treated with 3-bromo-benzenesulfinic acid methyl ester solution (Example 24: step d, 1 g, 4.49 mmol, 10 mL of THF) in one portion at −78° C. and then stirred overnight at room temperature. Saturated ammonium chloride solution was added to the mixture and stirred for 30 minutes at room temperature. The reaction mixture was diluted with ethyl acetate and washed with water and brine. The organic layer was dried over magnesium sulfate, filtered, concentrated in vacuo, and purified by column chromatography (silica gel, 15-25% ethyl acetate/hexanes) to afford the title compound as a light yellow solid (1.33 g, 85% yield). 1H-NMR (CDCl3): δ 7.86-7.88 (m, 1H), 7.69 (dm, 1H, J=7.9 Hz), 7.64 (dm, 1H, J=7.9 Hz), 7.62 (s, 1H), 7.42 (t, 1H, J=7.9 Hz).

Workup

  1. stirringstirred for 30 minutes at room temperature
  2. washwashed with water and brine
  3. dry with materialThe organic layer was dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. custompurified by column chromatography (silica gel, 15-25% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-9e8249d561154772ab87c5847054fa44
Source dataset
uspto-grants-2008_06
Patent number
US07385066B2

Reaction notes

Loading…