Hydrochloric Acid → HCID 58121069, compound

HRID 1186703Notes

Reaction equation

HRID 1186703 reaction equation
N[C:2]1[CH:6]=[C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[S:4][C:3]=1[C:13]([O:15][CH3:16])=[O:14].N([O-])=O.[Na+].[ClH:21]>O.Cl[Cu]>[Cl:21][C:2]1[CH:6]=[C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[S:4][C:3]=1[C:13]([O:15][CH3:16])=[O:14]

Participants

6

Reactant 3

HCID 313Hydrochloric Acid2×HCID 700562Methyl 3-amino-5-phenylthiophene-2-carboxylateHCID 23668193Sodium Nitrite

Product 1

HCID 58121069HCID 58121069, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent2×

Procedure

To a stirring solution of methyl 3-amino-5-phenylthiophene-2-carboxylate 82 (1.166 g, 5 mmol) in water (14 mL) and concentrated hydrochloric acid (7 mL) cooled to 0° C. was added a solution of sodium nitrite (0.431 g, 6.25 mmol) in water (2 mL). The reaction mixture was stirred for 30 min then the resulting solution was poured into a solution of CuCl (1.732 g, 17.50 mmol) in concentrated hydrochloric acid (20 mL) still at 0° C. The reaction was allowed to slowly warm to room temperature over 4 h then poured into ice cold water and extracted with ether (3×). The combined organic phases were washed with water, dried over Na2SO4, filtered and concentrated under reduced pressure to afford methyl 3-chloro-5-phenylthiophene-2-carboxylate 83 as a white solid (0.850 mg, 67% yield) after purification by ISCO (40 g column, 5 to 40% ethyl acetate in hexane). LRMS (ESI): (calc) 252.72 (found) 253.06 (MH)+

Workup

  1. additionthen poured into ice cold water
  2. extractionextracted with ether (3×)
  3. washThe combined organic phases were washed with water
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-15124ab5d28c47eda18581d65c8729f5
Source dataset
uspto-grants-2014_03
Patent number
US08673911B2

Reaction notes

Loading…