2-Nitroethanol → 6-Bromo-3-nitro-chroman

HRID 1986620

반응식

HRID 1986620 반응식
[Br:1][C:2]1[CH:9]=[C:6]([CH:7]=O)[C:5]([OH:10])=[CH:4][CH:3]=1.[Cl-].[CH2:12]([NH2+:16]CCCC)[CH2:13]CC.[N+:21]([CH2:24][CH2:25][OH:26])([O-:23])=[O:22].[BH3-]C#N.[Na+]>C(OCCCCC)(=O)C.O>[Br:1][C:2]1[CH:9]=[C:6]2[C:5](=[CH:4][CH:3]=1)[O:10][CH2:13][CH:12]([NH2:16])[CH2:7]2.[Br:1][C:2]1[CH:9]=[C:6]2[C:5](=[CH:4][CH:3]=1)[O:26][CH2:25][CH:24]([N+:21]([O-:23])=[O:22])[CH2:7]2

참가 물질

8

반응물 4

HCID 122522-NitroethanolHCID 728635-BromosalicylaldehydeHCID 517667N-butylbutan-1-amine hydrochlorideHCID 5003444Sodium cyanoborohydride

생성물 2

HCID 162444326-Bromochroman-3-amineHCID 221377596-Bromo-3-nitro-chroman수율 74.1%

시약·촉매·용매 2

HCID 962Water용매HCID 12348Amyl Acetate용매

실험 절차

6-Bromo-chroman-3-ylamine was prepared according to the literature procedure described by Andersson, B. R. et al. WO9012795. Thus, a mixture of 5-bromosalicylaldehyde (9.5 g, 47 mmol), di-n-butylammonium chloride (3.8 g, 23 mmol), and 2-nitroethanol (6.8 g, 75 mmol) in amyl acetate (60 mL) was heated at reflux for 3 hours with a Dean-Stark apparatus under nitrogen atmosphere. The solvent was removed in vacuo and the product was dissolved in CH2Cl2 (280 mL) followed by the addition of NaCNBH3 (9.6 g, 150 mmol). The mixture was stirred for 30 minutes and water (100 mL) was added to quench the reaction. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (50 mL×3). The combined organic layers were washed with brine, dried (Na2SO4), and concentrated in vacuo. The crude product was chromatographed on silica gel by eluting with 1:1 hexane/CH2Cl2 to give 4.4 g (40%) of pure 6-bromo-3-nitro-chroman as a light yellow solid. 1H NMR (300 MHz, CDCl3): δ 7.18 (m, 2H), 6.68 (d, J=8.4 Hz, 1H), 4.88 (m, 1H), 4.62 (m, 1H), 4.32 (m, 1H), 4.47 (m, 1H), 3.28 (dd, J=17.4, 6.0 Hz, 1H).

후처리

  1. temperaturewas heated
  2. temperatureat reflux for 3 hours with a Dean-Stark apparatus under nitrogen atmosphere
  3. customThe solvent was removed in vacuo
  4. dissolutionthe product was dissolved in CH2Cl2 (280 mL)
  5. customto quench
  6. customthe reaction
  7. customThe organic layer was separated
  8. extractionthe aqueous layer was extracted with CH2Cl2 (50 mL×3)
  9. washThe combined organic layers were washed with brine
  10. dry with materialdried (Na2SO4)
  11. concentrationconcentrated in vacuo
  12. customThe crude product was chromatographed on silica gel
  13. washby eluting with 1:1 hexane/CH2Cl2

출처 및 근거

ORD 기록
ord-1a1b221234b84a6da6d11bdcd5ae93eb
출처 데이터셋
uspto-grants-2009_06
특허 번호
US07550467B2

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