反応式
O(P([CH2:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])(OC1C=CC=CC=1)=O)C1C=CC=CC=1.[H-].[Na+].[Br:27][C:28]1[CH:29]=[C:30]([CH:35]=[C:36]([Br:40])[C:37]=1[CH:38]=O)[C:31]([O:33][CH3:34])=[O:32]>C1COCC1>[Br:27][C:28]1[CH:29]=[C:30]([CH:35]=[C:36]([Br:40])[C:37]=1/[CH:38]=[CH:17]\[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:31]([O:33][CH3:34])=[O:32]参加物
反応条件
- 温度
- -78 °C
実験手順
To a solution of tert-butyl (diphenoxyphosphoryl)acetate (267 mg) in THF (7.5 mL) at 0° C. under nitrogen was added sodium hydride and the mixture stirred for 15 min until gas evolution ceased. This anion mixture was then cooled to −78° C. and a solution of methyl 3,5-dibromo-4-formylbenzoate (262 mg) in THF (7.5 mL) was added dropwise. The reaction mixture was stirred at −78° C. for an additional 40 min before being quenched with saturated ammonium chloride solution, extracted into ethyl acetate, dried over MgSO4 and concentrated. The residue was purified by column chromatography on silica gel eluting with 90% hexane:10% ethyl acetate to give the title compound which also contained 20% of the E double-bond isomer. No attempt was made to separate these isomers at this stage. 1H NMR (500 MHz, CDCl3): 88.23 (s, 1H, E isomer); 8.21 (s, 1H, Z isomer); 7.57 (d, J=16.3 Hz, 1H, E isomer); 6.76 (d, J=11.9 Hz, 1H, Z isomer); 6.38 (d, J=16.3 Hz, 1H E isomer); 6.12 (d, J=11.9 Hz, 1H Z isomer); 3.954 (s, 3H, E isomer); 3.948 (s, 3H, Z isomer); 1.28 (s, 9H, both isomers). Mass spectrum: m/z 365 (M+H-t-Bu).
後処理
- stirringThe reaction mixture was stirred at −78° C. for an additional 40 min
- custombefore being quenched with saturated ammonium chloride solution
- extractionextracted into ethyl acetate
- dry with materialdried over MgSO4
- concentrationconcentrated
- customThe residue was purified by column chromatography on silica gel eluting with 90% hexane
出典と根拠
- ORDレコード
- ord-0ba89197d0b34a4baaf4efa435e5d758
- 出典データセット
- uspto-grants-2004_10
- 特許番号
- US06809199B2
関連ノート
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