Sodium hydride → Methyl 3,5-dibromo-4-[(1Z)-3-tert-butoxy-3-oxoprop-1-enyl]benzoate

HRID 394207

반응식

HRID 394207 반응식
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]

참가 물질

5

반응물 3

HCID 24758Sodium hydrideHCID 10689048Tert-butyl (diphenoxyphosphoryl)acetateHCID 22647908Methyl 3,5-dibromo-4-formylbenzoate

생성물 1

HCID 69919932Methyl 3,5-dibromo-4-[(1Z)-3-tert-butoxy-3-oxoprop-1-enyl]benzoate

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-78 °C

실험 절차

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).

후처리

  1. stirringThe reaction mixture was stirred at −78° C. for an additional 40 min
  2. custombefore being quenched with saturated ammonium chloride solution
  3. extractionextracted into ethyl acetate
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography on silica gel eluting with 90% hexane

출처 및 근거

ORD 기록
ord-0ba89197d0b34a4baaf4efa435e5d758
출처 데이터셋
uspto-grants-2004_10
특허 번호
US06809199B2

연결된 노트

불러오는 중…