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

HRID 2298619ノート

反応式

HRID 2298619 の反応式
[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

参加物

5

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 160960Diamminetetrachlorotitanate(IV)触媒HCID 8028Tetrahydrofuran溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-22a7ba07a67a4956aaa43d005da11dfe
出典データセット
uspto-grants-2002_12
特許番号
US06492403B1

反応ノート

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