Sodium Carbonate → 3-(4,4-Dimethyl-2-oxo-2,4-dihydro-1H-benzo[D][1,3]oxazin-6-YL)benzonitrile

HRID 50671

반응식

HRID 50671 반응식
[CH3:1][C:2]1([CH3:16])[C:7]2[CH:8]=[C:9](B(O)O)[CH:10]=[CH:11][C:6]=2[NH:5][C:4](=[O:15])[O:3]1.Br[C:18]1[CH:19]=[C:20]([CH:23]=[CH:24][CH:25]=1)[C:21]#[N:22].C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1([CH3:16])[O:3][C:4](=[O:15])[NH:5][C:6]2[CH:11]=[CH:10][C:9]([C:18]3[CH:19]=[C:20]([CH:23]=[CH:24][CH:25]=3)[C:21]#[N:22])=[CH:8][C:7]1=2

참가 물질

7

반응물 3

HCID 10340Sodium CarbonateHCID 233813-BromobenzonitrileHCID 10987806(4,4-Dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)boronic acid

생성물 1

HCID 98142163-(4,4-Dimethyl-2-oxo-2,4-dihydro-1H-benzo[D][1,3]oxazin-6-YL)benzonitrile수율 25.2%

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 80711,2-Dimethoxyethane용매

반응 조건

온도
85 °C

실험 절차

A mixture of (1,4-dihydro-4,4-dimethyl-2-oxo-2H-3,1-benzoxazin-6-yl)boronic acid (2.22 g, 10 mmol), 3-bromobenzonitrile (2.18 g, 12 mmol), tetrakis(triphenylphosphine)palladium (0) (0.6 g, 0.52 mmol), and sodium carbonate (2.2 g, 21 mmol) in a mixture of DME and water (70 mL/15 mL) was degassed to remove the oxygen and then heated at 85° C. under a blanket of nitrogen for 3 hours. The reaction mixture was cooled to ambient temperature and quenched with a saturated aqueous ammonium chloride solution (20 mL). Ethyl acetate (100 mL) was added and organic layer was separated. The aqueous layer was extracted with ethyl acetate (3×30 mL). The combined organic layers were washed with brine and dried with MgSO4. The solvent was removed in vacuo and the residue was purified by a silica gel flash chromatography (hexane ethyl acetate/1:1) to give 3-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-6-yl)-benzonitrile as an off-white solid (0.7 g, 25%): mp 236-237° C.; 1H-NMR (DMSO-d6) δ 10.34 (s, 1H, D2O exchangeable), 8.21 (s, 1H), 8.02 (d, 1H, J=8.1 Hz), 7.79 (d, 1H, J=7.7 Hz), 7.60-7.70 (m, 3H), 6.98 (d, 1H, J=8.2 Hz), 1.71 (s, 6H), Anal. Calc. For C17H14N2H2O: C, 72.89; H, 5.11; N, 10.00. Found: C, 72.75; H, 5.05; N, 9.65.

후처리

  1. customwas degassed
  2. customto remove the oxygen
  3. temperatureThe reaction mixture was cooled to ambient temperature
  4. customquenched with a saturated aqueous ammonium chloride solution (20 mL)
  5. additionEthyl acetate (100 mL) was added
  6. customorganic layer was separated
  7. extractionThe aqueous layer was extracted with ethyl acetate (3×30 mL)
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried with MgSO4
  10. customThe solvent was removed in vacuo
  11. customthe residue was purified by a silica gel flash chromatography (hexane ethyl acetate/1:1)

출처 및 근거

ORD 기록
ord-47ac750880e442a1854d40edb668bf94
출처 데이터셋
uspto-grants-2004_03
특허 번호
US06713478B2

연결된 노트

불러오는 중…