Hydrochloric Acid → ethyl 8-chloro-4-hydroxy-2-oxo-2',3',5',6'-tetrahydro-4H-spiro[naphthalene-1,4'-pyran]-3-carboxylate

HRID 1868940ノート

反応式

HRID 1868940 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4](/[C:8](/[OH:15])=[CH:9]/[C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:3]=1[C:16]1([C:22](OCC)=[O:23])[CH2:21][CH2:20][O:19][CH2:18][CH2:17]1.CC[O-].[Na+].Cl>CCO.CCOC(C)=O>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]2[C:3]=1[C:16]1([CH2:17][CH2:18][O:19][CH2:20][CH2:21]1)[C:22](=[O:23])[CH:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:8]2[OH:15]

参加物

6

反応物 3

HCID 313Hydrochloric AcidHCID 2723922Sodium ethoxideHCID 86629261(Z)-ethyl 4-(2-chloro-6-(3-ethoxy-1-hydroxy-3-oxoprop-1-enyl)phenyl)-tetrahydro-2H-pyran-4-carboxylate

生成物 1

HCID 67099930ethyl 8-chloro-4-hydroxy-2-oxo-2',3',5',6'-tetrahydro-4H-spiro[naphthalene-1,4'-pyran]-3-carboxylate収率 80.5%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
60 °C

実験手順

A mixture of (Z)-ethyl 4-(2-chloro-6-(3-ethoxy-1-hydroxy-3-oxoprop-1-enyl)phenyl)-tetrahydro-2H-pyran-4-carboxylate (0.38 g, 0.99 mmol) in 5 mL EtOH was treated with NaOEt (freshly made from 0.1 g Na and 5 mL EtOH), and stirred at 60° C. for 2 hours. The mixture was cooled to room temperature and diluted with 100 mL EtOAc, neutralized with 5N HCl to pH 5, washed with water (20 mL), saturated NaCl (20 mL), dried over anhydrous sodium sulfate and concentrated. The concentrate was purified by column chromatography (10-40% EtOAc/hexane) to give 0.27 g yellow solid. MS m/e: (M+H)+ 337.

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. washwashed with water (20 mL), saturated NaCl (20 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated
  5. customThe concentrate was purified by column chromatography (10-40% EtOAc/hexane)

出典と根拠

ORDレコード
ord-05d9249ad98a4b828a33d99ec5771dec
出典データセット
uspto-grants-2009_12
特許番号
US07635715B2

反応ノート

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