Cesium carbonate → Dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-YL)phosphine oxide

HRID 39607

반응식

HRID 39607 반응식
BrC1C=CC=CC=1[O:8]C.C(=O)([O-])[O-].[Cs+].[Cs+].[CH:16]1([P:22]([CH:39]2[CH2:44][CH2:43][CH2:42][CH2:41][CH2:40]2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[C:29]2[C:34]([O:35][CH3:36])=[CH:33][CH:32]=[CH:31][C:30]=2[O:37][CH3:38])[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1.O.NN>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.CO.O1CCOCC1>[CH:39]1([P:22]([CH:16]2[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]2)([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[C:29]2[C:34]([O:35][CH3:36])=[CH:33][CH:32]=[CH:31][C:30]=2[O:37][CH3:38])=[O:8])[CH2:40][CH2:41][CH2:42][CH2:43][CH2:44]1

참가 물질

10

반응물 4

HCID 10796Cesium carbonateHCID 113582-BromoanisoleHCID 24654Hydrazine hydrate (1:1)HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

생성물 1

HCID 67122844Dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-YL)phosphine oxide수율 45.4%

시약·촉매·용매 5

HCID 167845palladium(II) acetate촉매HCID 887Methanol용매HCID 962Water용매2회HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

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온도
95 °C

실험 절차

To the mixture of 2-bromoanisole (0.020 ml, 0.16 mmol) and 1,4-dioxane (2 ml), water (0.2 ml), cesium carbonate (0.32 g, 0.97 mmol), sodium 1,3-dioxo-1,3-dihydro-isoindole-2-ylmethyl trifluoroborate (81 mg, 0.32 mmol), palladium(II) acetate (3.6 mg, 0.016 mmol), and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (13 mg, 0.032 mmol) were added, and then the obtained reaction mixture was stirred at 95° C. (an outer temperature) overnight. The reaction mixture was cooled to room temperature, and then hydrazine hydrate (0.039 ml, 0.81 mmol) and methanol (2 ml) were added thereto, followed by heating to reflux for 1 hour. The reaction mixture was cooled to room temperature, and then water and ethyl acetate were added to the reaction mixture, followed by filtration with celite. The organic layer of the filtrate was separated and washed with saline. The solvents were evaporated under reduced pressure from the organic layer, and then the obtained residue was purified with NH-silica gel column chromatography (heptane:ethyl acetate=1:4), thereby obtaining the entitled compound (4.1 mg, 19%) as the mixture with 2′-(dicyclohexyl-phosphinoyl)-2,6-dimethoxy-biphenyl (6.2 mg).

후처리

  1. additionwere added
  2. customthe obtained reaction mixture
  3. temperatureThe reaction mixture was cooled to room temperature
  4. temperatureby heating
  5. temperatureto reflux for 1 hour
  6. temperatureThe reaction mixture was cooled to room temperature
  7. filtrationfollowed by filtration with celite
  8. customThe organic layer of the filtrate was separated
  9. washwashed with saline
  10. customThe solvents were evaporated under reduced pressure from the organic layer
  11. customthe obtained residue was purified with NH-silica gel column chromatography (heptane:ethyl acetate=1:4)

출처 및 근거

ORD 기록
ord-d01713c474f74d42b87c525175407e98
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08524946B2

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