Toluene → 3-(1-ethyl-4,4,6-trimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-7-yl)-4-trifluoromethoxy-benzaldehyde

HRID 2239251

反応式

HRID 2239251 の反応式
Br[C:2]1[C:3]([CH3:17])=[CH:4][C:5]2[C:10]([CH3:12])([CH3:11])[O:9][C:8](=[O:13])[N:7]([CH2:14][CH3:15])[C:6]=2[CH:16]=1.[F:18][C:19]([F:33])([F:32])[O:20][C:21]1[CH:26]=[CH:25][C:24]([CH:27]=[O:28])=[CH:23][C:22]=1B(O)O.C1(C)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+]>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.C(O)C>[CH2:14]([N:7]1[C:6]2[CH:16]=[C:2]([C:26]3[CH:25]=[C:24]([CH:23]=[CH:22][C:21]=3[O:20][C:19]([F:18])([F:32])[F:33])[CH:27]=[O:28])[C:3]([CH3:17])=[CH:4][C:5]=2[C:10]([CH3:12])([CH3:11])[O:9][C:8]1=[O:13])[CH3:15]

参加物

7

反応物 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 219664285-Formyl-2-(trifluoromethoxy)benzeneboronic acidHCID 685829667-Bromo-1-ethyl-4,4,6-trimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one

生成物 1

HCID 866116793-(1-ethyl-4,4,6-trimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-7-yl)-4-trifluoromethoxy-benzaldehyde収率 52%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 702Ethanol溶媒

反応条件

温度
80 °C

実験手順

A round bottom flask was charged with 0.5 g (1.67 mmol) of Compound 14D, 0.58 g (2,5 mmol) of 2-trifluoromethoxy-5-formylphenylboronic acid and 0.083 g of tetrakis(triphenylphosphine)palladium(0). The flask was sealed with a septa and 8.5 mL of toluene and 2.5 mL of ethanol was added. The resulting solution was stirred to dissolve the reactants and then 1.7 mL of 2M K2CO3 was added via syringe. The reaction mixture was heated to 80° C. for 4 hours. After cooling, the reaction mixture was partitioned between ethyl acatate (20 mL) and water (8 mL). The water layer was further extracted (2×10 mL) and the combined organic layers were washed with water (10 mL) followed by brine (10 mL), dried over magnesium sulfate, filtered and excess solvent removed on the rotary evaporator. The crude product was purified by flash chromatography (EtOAc/Hexanes; gradient 20% to 40%) to give 0.35 g (52%) of 3-(1-ethyl-4,4,6-trimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-7-yl)-4-trifluoromethoxy-benzaldehyde as yellow solid. MS (electrospray): mass calculated for C21H20F3NO4, 407.13; m/z found 408 [M+H]+.

後処理

  1. additionwas added
  2. dissolutionto dissolve the reactants
  3. temperatureAfter cooling
  4. customthe reaction mixture was partitioned between ethyl acatate (20 mL) and water (8 mL)
  5. extractionThe water layer was further extracted (2×10 mL)
  6. washthe combined organic layers were washed with water (10 mL)
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customexcess solvent removed on the rotary evaporator
  10. customThe crude product was purified by flash chromatography (EtOAc/Hexanes; gradient 20% to 40%)

出典と根拠

ORDレコード
ord-c0042d7720d44d08978f2de0f3d5c9b2
出典データセット
uspto-grants-2010_05
特許番号
US07723326B2

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