Potassium Phosphate, Tribasic → 8-Allyl-2-methyl-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazine-6-carbaldehyde

HRID 1184488ノート

反応式

HRID 1184488 の反応式
P([O-])([O-])([O-])=O.[K+].[K+].[K+].[CH2:9]([B-](F)(F)F)[CH:10]=[CH2:11].[K+].Cl[C:18]1[C:23]2[O:24][CH:25]([CH3:29])[C:26](=[O:28])[NH:27][C:22]=2[CH:21]=[C:20]([CH:30]=[O:31])[CH:19]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC(C)C)=CC=CC=2OC(C)C)CCCCC1>C1(C)C=CC=CC=1.O>[CH2:11]([C:18]1[C:23]2[O:24][CH:25]([CH3:29])[C:26](=[O:28])[NH:27][C:22]=2[CH:21]=[C:20]([CH:30]=[O:31])[CH:19]=1)[CH:10]=[CH2:9]

参加物

7

反応物 4

HCID 62657Potassium Phosphate, TribasicHCID 162179852-Dicyclohexylphosphino-2',6'-diisopropoxybiphenylHCID 23664277Potassium AllyltrifluoroborateHCID 866642218-Chloro-2-methyl-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazine-6-carbaldehyde

生成物 1

HCID 866642248-Allyl-2-methyl-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazine-6-carbaldehyde収率 3.41%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 1140Toluene溶媒

反応条件

温度
115 °C

実験手順

To a solution of potassium phosphate, tribasic (0.564 g, 2.66 mmol), potassium allyltrifluoroborate (0.197 g, 1.330 mmol), and 8-chloro-2-methyl-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazine-6-carbaldehyde 15 (0.2 g, 0.886 mmol) in toluene (Ratio: 5.00, 20 mL) and water (Ratio: 1.000, 4.0 mL) was added PdOAc2 (0.015 g, 0.066 mmol) and dicyclohexyl(2′,6′-diisopropoxybiphenyl-2-yl)phosphine (0.062 g, 0.133 mmol) at 23° C. The reaction was stirred at 115° C. for 48 hr. The reaction mixture was poured into water (2 mL) and extracted with Et2O (3×5 mL). The organic layer was dried over Na2SO4, filtered, and the organic phase stripped to dryness via rotary evaporation. The resulting crude material was reconstituted in DCM (0.25 mL) and purified via medium pressure chromatography using a gradient eluant of 1-5% MeOH:DCM. The appropriate fractions were combined and solvent was removed via rotary evaporation. The impure material was reconstituted in DMSO (1.0 mL) and purified via preparative mass trigger LCMS using a gradient eluant of 45-70% ACN:0.05% TFA (aq). The collected fractions were combined and the solvent was removed via rotary evaporation to provide the title compound as an off-white solid (0.007 g, 0.030 mmol, 3.41% yield). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.44 (d, J=6.82 Hz, 3H) 3.38-3.42 (m, 2H) 4.82 (q, J=6.82 Hz, 1H) 5.06-5.12 (m, 2H) 5.91-6.01 (m, 1H) 7.28 (d, J=2.02 Hz, 1H) 7.42 (d, J=2.02 Hz, 1H) 9.82 (s, 1H) 10.93 (s, 1H). ESI-MS: m/z 232.2 (M+H)+.

後処理

  1. customat 23° C
  2. extractionextracted with Et2O (3×5 mL)
  3. dry with materialThe organic layer was dried over Na2SO4
  4. filtrationfiltered
  5. customthe organic phase stripped to dryness via rotary evaporation
  6. custompurified via medium pressure chromatography
  7. customsolvent was removed via rotary evaporation
  8. custompurified via preparative mass trigger LCMS
  9. customthe solvent was removed via rotary evaporation

出典と根拠

ORDレコード
ord-2baeb129f90e4358898d5c37e198611e
出典データセット
uspto-grants-2014_03
特許番号
US08669249B2

反応ノート

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