Hydrochloric Acid → 5-Hydroxy-2-(3-methyl-butyl)-3-oxo-6-thiophen-2-yl-2,3-dihydro-pyridazine-4-carboxylic acid ethyl ester

HRID 30978ノート

反応式

HRID 30978 の反応式
C(O[C:4](=[O:26])[C:5](=[N:11][N:12]([C:18](=[O:25])[CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:13][CH2:14][CH:15]([CH3:17])[CH3:16])[C:6]1[S:7][CH:8]=[CH:9][CH:10]=1)C.[O-]CC.[Na+].Cl>CCO>[CH2:23]([O:22][C:20]([C:19]1[C:18](=[O:25])[N:12]([CH2:13][CH2:14][CH:15]([CH3:16])[CH3:17])[N:11]=[C:5]([C:6]2[S:7][CH:8]=[CH:9][CH:10]=2)[C:4]=1[OH:26])=[O:21])[CH3:24]

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 2723922Sodium ethoxideHCID 72394125[(2-Ethoxycarbonyl-acetyl)-(3-methyl-butyl)-hydrazono]-thiophen-2-yl-acetic acid ethyl ester

生成物 1

HCID 597914415-Hydroxy-2-(3-methyl-butyl)-3-oxo-6-thiophen-2-yl-2,3-dihydro-pyridazine-4-carboxylic acid ethyl ester収率 83.2%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

To a solution of [(2-Ethoxycarbonyl-acetyl)-(3-methyl-butyl)-hydrazono]-thiophen-2-yl-acetic acid ethyl ester (12a) (380 mg, 1.0 mmol) in EtOH (6 mL) at room temperature, sodium ethoxide (Aldrich) (21 wt % in ethanol, 0.4 mL, 1.1 mmol) was added, and the resulting mixture was stirred for 30 min. Aqueous HCl (5%, 0.75 mL) was added slowly, and then followed by liquid-liquid extraction with H2O/EtOAc. The combined organic layer was washed with brine, dried over MgSO4, concentrated under reduced pressure and the residue was purified by flash chromatography on silica gel to give the desired product (13a) (280 mg, 83%) as yellow solid. LC-MS (ESI+): m/e=337.30 [M+1]+(exact ms: 336.11); 1H NMR (400 MHz, CDCl3): δ 7.89 (dd, 1H, J=3.6, 1.2 Hz), 7.39 (dd, 1H, J=5.2, 1.2 Hz), 7.10 (dd, 1H, J=5.2, 3.6 Hz), 4.53 (q, 2H, J=7.2 Hz), 4.22 (m, 2H), 1.73 (m, 2H), 1.68 (m, 1H), 1.50 (t, 3H, J=7.2 Hz), 0.99 (d, 6H, J=6.4 Hz).

後処理

  1. extractionfollowed by liquid-liquid extraction with H2O/EtOAc
  2. washThe combined organic layer was washed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated under reduced pressure
  5. customthe residue was purified by flash chromatography on silica gel

出典と根拠

ORDレコード
ord-a4c0df31ae8940cabdc18cf7376b4cc7
出典データセット
uspto-grants-2008_09
特許番号
US07425552B2

反応ノート

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