Binap, (A+-)- → 8-Bromo-3,4-dihydro-2H-1,4-benzoxazine

HRID 388289노트

반응식

HRID 388289 반응식
C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+].[Br:53][C:54]1[CH:63]=[CH:62][CH:61]=[C:60](Br)[C:55]=1[O:56][CH2:57][CH2:58][NH2:59]>C1(C)C=CC=CC=1.C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:53][C:54]1[C:55]2[O:56][CH2:57][CH2:58][NH:59][C:60]=2[CH:61]=[CH:62][CH:63]=1

참가 물질

7

반응물 3

HCID 634876Binap, (A+-)-HCID 225572812-(2,6-Dibromo-phenoxy)ethylamineHCID 23676156Sodium t-butoxide

생성물 1

HCID 162444528-Bromo-3,4-dihydro-2H-1,4-benzoxazine수율 48%

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

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온도
95 °C

실험 절차

A three neck flask was charge with tris(dibenzylideneacetone)dipalladium(0) (0.37 g, 0.0004 mol, 2 mol % Pd), (±) racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.64 g, 0.001 mol, 5 mol % Pd), and sodium tert-butoxide (2.7 g, 0.028 mol) and flushed with nitrogen. A solution of 2-(2,6-dibromo-phenoxy)ethylamine (6 g, 0.02 mol) in toluene (50 mL) was added. The mixture was heated to 95° C. and was stirred for 12 h. The mixture was cooled to room temperature, taken up in ethyl acetate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (eluting with hexane-ethyl acetate; 7:3, v/v) to give 8-bromo-3,4-dihydro-2H-benzo[1,4]oxazine as an oil (275 mg, 48%). The hydrochloride salt was prepared from ethanol-hydrogen chloride. MS: MH+=214. M.p. 184.1-195.4° C.

후처리

  1. customflushed with nitrogen
  2. temperatureThe mixture was cooled to room temperature
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude material was purified by flash chromatography on silica gel (
  6. washeluting with hexane-ethyl acetate

출처 및 근거

ORD 기록
ord-ac46deb7121a448ba19a56a280184319
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08377931B2

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