Ammonia → Methyl 4-aminothiophene-3-carboxylate

HRID 2380777Notes

Reaction equation

HRID 2380777 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[C:9](=O)[CH2:8][S:7][CH2:6]1)=[O:4].[NH2:11]O.N>>[NH2:11][C:9]1[C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:6][S:7][CH:8]=1

Participants

4

Reactant 3

HCID 222AmmoniaHCID 787HydroxylamineHCID 984243-Thiophenecarboxylic acid, tetrahydro-4-oxo-, methyl ester

Product 1

HCID 2777610Methyl 4-aminothiophene-3-carboxylate

Procedure

Diazotization of methyl 4-aminothiophene-3-carboxylate with sodium nitrite followed by treatment with dimethylamine provides methyl 4-[(dimethylamino)diazenyl]thiophene-3-carboxylate. Treatment of the ester with ammonia gave the required 4-[dimethylamino)diazenyl]thiophene-3-carboxamide (compd. No. 13). The methyl 4-aminothiophene-3-carboxylate is produced using known procedures in the prior art (33, 34, 35). Thus addition of methyl acrylate to methyl thioglycolate provided methyl 3-[(methoxycarbonyl)methylthio]propanoate in quantitative yield, which on cyclization in presence of sodium methoxide gave methyl 4-oxo-2,3,5-trihydrothiophene-3-carboxylate. Treatment of methyl 4-oxo-2,3,5-trihydrothiophene-3-carboxylate with hydroxylamine followed by basification with ammonia gave methyl 4-aminothiophene-3-carboxylate.

Sources & evidence

ORD record
ord-b8422c6e9b4748fc896b3462859076a5
Source dataset
uspto-grants-2012_09
Patent number
US08258119B2

Reaction notes

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