Sodium Hydroxide → Methyl 4-(4-(4-aminophenyl)(1,3-thiazol-2-yl))-5-methylthiothiophene-2-carboxylate

HRID 2298619Notes

Reaction equation

HRID 2298619 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[N:11]=[C:12]([C:15]3[CH:16]=[C:17]([C:21]([O:23][CH3:24])=[S:22])[S:18][C:19]=3[CH3:20])[S:13][CH:14]=2)=[CH:6][CH:5]=1)([O-])=O.[OH-].[Na+]>O1CCCC1.[Cl-].[Ti+4].[Cl-].[Cl-].[Cl-]>[NH2:1][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[N:11]=[C:12]([C:15]3[CH:16]=[C:17]([C:21]([O:23][CH3:24])=[S:22])[S:18][C:19]=3[CH3:20])[S:13][CH:14]=2)=[CH:6][CH:5]=1

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 86758673Methyl 4-(4-(4-nitrophenyl)(1,3-thiazol-2-yl))-5-methylthiothiophene-2-carboxylate

Product 1

HCID 86583820Methyl 4-(4-(4-aminophenyl)(1,3-thiazol-2-yl))-5-methylthiothiophene-2-carboxylateYield 72.2%

Reagents, catalysts & solvents 2

HCID 160960Diamminetetrachlorotitanate(IV)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

Methyl 4-(4-(4-nitrophenyl)(1,3-thiazol-2-yl))-5-methylthiothiophene-2-carboxylate (800 mg, 2 mmol) was dissolved in 150 mL tetrahydrofuran and treated with 20% titanium chloride solution (Fisher Scientific, Pittsburgh, Pa., USA) for 1 h. The mixture was poured into 2 M sodium hydroxide solution (100 mL), extracted with dichloromethane (4×50 mL). The combined organic layers were washed with saturated brine solution and dried over anhydrous sodium sulfate. The solid was filtered off, and the solvent removed in vacuo. This material was purified by column chromatography on silica gel (30 g) eluting with dichloromethane:methanol 98/2 (v:v) to give methyl 4-(4-(4-aminophenyl)(1,3-thiazol-2-yl))-5-methylthiothiophene-2-carboxylate (500 mg, 69%) as a solid. 1H-NMR (DMSO-d6; 300 MHz) δ8.17 (s, 1H), 7.77 (s, 1H), 7.74 and 6.62 (AB quartet, 2H, J=8.6 Hz), 5.35 (s, 2H), 3.86 (s, 3H), 2.74 (s, 3H). ). Mass spectrum (MALDI-TOF, CHCA matrix, m/z): Calcd. for C16H14N2O2S3 363.0 (M+H), found 362.4.

Workup

  1. extractionextracted with dichloromethane (4×50 mL)
  2. washThe combined organic layers were washed with saturated brine solution
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationThe solid was filtered off
  5. customthe solvent removed in vacuo
  6. customThis material was purified by column chromatography on silica gel (30 g)
  7. washeluting with dichloromethane

Sources & evidence

ORD record
ord-22a7ba07a67a4956aaa43d005da11dfe
Source dataset
uspto-grants-2002_12
Patent number
US06492403B1

Reaction notes

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