Methanol → Acetic acid, 2-[4-(4-bromophenyl)-4-hydroxycyclohexylidene]-, methyl ester

HRID 881766노트

반응식

HRID 881766 반응식
[H-].[Na+].C[C:4](P(OC)(O)=O)([C:6]([O-:8])=[O:7])[CH3:5].[Br:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]2([OH:28])[CH2:26][CH2:25][C:24](=O)[CH2:23][CH2:22]2)=[CH:17][CH:16]=1.[CH3:29]O>>[Br:14][C:15]1[CH:16]=[CH:17][C:18]([C:21]23[O:28][C:5]([CH2:4][C:6]([O:8][CH3:29])=[O:7])([CH2:25][CH2:26]2)[CH2:23][CH2:22]3)=[CH:19][CH:20]=1.[Br:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]2([OH:28])[CH2:26][CH2:25][C:24](=[CH:4][C:6]([O:8][CH3:29])=[O:7])[CH2:23][CH2:22]2)=[CH:17][CH:16]=1

참가 물질

6

반응물 4

HCID 887MethanolHCID 24758Sodium hydrideHCID 53413272TrimethylphosphonoacetateHCID 67715663HCID 67715663, 화합물

생성물 2

HCID 86700872HCID 86700872, 화합물수율 12%HCID 86700873Acetic acid, 2-[4-(4-bromophenyl)-4-hydroxycyclohexylidene]-, methyl ester수율 63%

실험 절차

To a solution of NaH (60% dispersion in mineral oil, 70 mg, 1.7 mmol) in methanol (6.7 mL) was added trimethylphosphonoacetate (0.23 mL, 1.6 mmol) and the reaction was let stir at rt for 30 min. To the reaction was added 4-(4-bromophenyl)-4-hydroxycyclohexanone (360 mg, 1.3 mmol) and the reaction was let stir at rt for 20 h. The resulting reaction mixture was quenched with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic phase was dried over MgSO4, filtered and concentrated by rotary evaporation in vacuo to afford 530 mg of a crude opaque oil. Purification of the crude material by column chromatography (25 g silica gel, 0-60% EtOAc:Hept, monitor 230 nm) afforded 51 mg (12%) of methyl 2-(4-(4-bromophenyl)-7-oxabicyclo[2.2.1]heptan-1-yl)acetate as a colorless oil (ESI-MS m/z: 327.1 [M+H]+, retention time 1.56 min (condition E)) and 275 mg (63%) of the title compound as a colorless oil (ESI-MS m/z: n/a [M+H]+, retention time 1.42 min (condition E)). 1H NMR (400 MHz, DMSO-d6): δ ppm 1.71-1.93 (m, 4H), 2.19 (d, J=13.1 Hz, 1H), 2.29-2.44 (m, 1H), 2.66 (td, J=12.6, 4.7 Hz, 1H), 3.56-3.69 (m, 4H), 5.24 (s, 1H), 5.72 (s, 1H), 7.41-7.52 (m, 4H). 13C NMR (100 MHz, DMSO-d6): δ ppm 166.1, 162.5, 148.7, 130.6, 127.1, 119.3, 112.6, 70.8, 50.6, 38.7, 32.4, 24.5.

후처리

  1. stirringthe reaction was let stir at rt for 20 h
  2. customThe resulting reaction mixture
  3. customwas quenched with saturated aqueous ammonium chloride solution
  4. extractionextracted with ethyl acetate
  5. dry with materialThe organic phase was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated by rotary evaporation in vacuo
  8. customto afford 530 mg of a crude opaque oil
  9. customPurification of the crude material by column chromatography (25 g silica gel, 0-60% EtOAc:Hept, monitor 230 nm)

출처 및 근거

ORD 기록
ord-722fafc44f284928aa38716c13d38e57
출처 데이터셋
uspto-grants-2015_03
특허 번호
US08993619B2

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