Hydrochloric Acid → HCID 71532156, compound

HRID 518134Notes

Reaction equation

HRID 518134 reaction equation
Br[C:2]1[CH:6]=[CH:5][S:4][C:3]=1[CH2:7][C:8]#[N:9].[CH:10](OCC)=O.[O-]CC.[Na+].C(O)C.Cl.[NH2:23][C:24]1[CH:32]=[CH:31][C:27]([C:28]([OH:30])=[O:29])=[C:26]([OH:33])[CH:25]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Cl>CS(C)=O.[Cu]I.C(O)CO.O>[C:8]([C:7]1[C:3]2[S:4][CH:5]=[CH:6][C:2]=2[N:23]([C:24]2[CH:32]=[CH:31][C:27]([C:28]([OH:30])=[O:29])=[C:26]([OH:33])[CH:25]=2)[CH:10]=1)#[N:9]

Participants

12

Reactant 7

HCID 313Hydrochloric AcidHCID 46494-Aminosalicylic AcidHCID 8025Ethyl formateHCID 62657Potassium Phosphate, TribasicHCID 2723922Sodium ethoxideHCID 18628861209796-27-0HCID 21887872Ethanol hydrochloride

Product 1

HCID 71532156HCID 71532156, compoundYield 32%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 174Ethylene GlycolSolventHCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent

Procedure

To a solution of 2-(3-bromothiophen-2-yl)acetonitrile (1.0 g) and ethyl formate (3.7 g) in dimethyl sulfoxide (5.0 mL) was added sodium ethoxide (20% solution in ethanol, 3.1 mL), and the mixture was stirred at room temperature for 3 hours. 2.5 mol/L hydrochloric acid ethanol solution (3.6 mL) and 4-amino-2-hydroxybenzoic acid (0.9 g) were added to reaction solution. The mixture was stirred at 50° C. for 5 hours. To the reaction solution was added water. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 50° C. for 3 hours. The obtained residue was purified by column chromatography on silica gel (eluent: dichloromethane/methanol=87/13−78/22) to give the condensate (0.91 g). To a solution of this condensate (0.91 g) in dimethyl sulfoxide (4.5 mL) were added copper(I) iodide (47 mg), ethylene glycol (0.3 g) and tripotassium phosphate (1.1 g), and the mixture was stirred at 80° C. for 5 hours. After cooling to 50° C., to the mixture was added 2 mol/L hydrochloric acid (8.7 mL) and the mixture was stirred at room temperature for 1 hour. The precipitated solid was collected by filtration, washed with mixed solution of water and dimethyl sulfoxide, 1 mol/L hydrochloric acid and water, and dried under reduced pressure at 50° C. to give the title compound (0.45 g).

Workup

  1. stirringThe mixture was stirred at 50° C. for 5 hours
  2. filtrationThe precipitated solid was collected by filtration
  3. washwashed with water
  4. customdried under reduced pressure at 50° C. for 3 hours
  5. customThe obtained residue was purified by column chromatography on silica gel (eluent: dichloromethane/methanol=87/13−78/22)
  6. customto give the condensate (0.91 g)
  7. stirringthe mixture was stirred at 80° C. for 5 hours
  8. temperatureAfter cooling to 50° C., to the mixture
  9. stirringthe mixture was stirred at room temperature for 1 hour
  10. filtrationThe precipitated solid was collected by filtration
  11. washwashed with mixed solution of water and dimethyl sulfoxide, 1 mol/L hydrochloric acid and water
  12. customdried under reduced pressure at 50° C.

Sources & evidence

ORD record
ord-91feb121955143cc810162568358f0bd
Source dataset
uspto-grants-2015_08
Patent number
US09115144B2

Reaction notes

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