Diethyl Ether → 6-(5-Acetyl-2-trifluoromethoxy-phenyl)-4-ethyl-2,2,7-trimethyl-4h-benzo[1,4]oxazin-3-one

HRID 2239249ノート

反応式

HRID 2239249 の反応式
[CH2:1]([N:3]1[C:8]2[CH:9]=[C:10]([C:14]3[CH:15]=[C:16]([CH:19]=[CH:20][C:21]=3[O:22][C:23]([F:26])([F:25])[F:24])[CH:17]=[O:18])[C:11]([CH3:13])=[CH:12][C:7]=2[O:6][C:5]([CH3:28])([CH3:27])[C:4]1=[O:29])[CH3:2].[CH3:30][Mg]Br.C(OCC)C.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C1COCC1>[C:17]([C:16]1[CH:19]=[CH:20][C:21]([O:22][C:23]([F:25])([F:24])[F:26])=[C:14]([C:10]2[C:11]([CH3:13])=[CH:12][C:7]3[O:6][C:5]([CH3:28])([CH3:27])[C:4](=[O:29])[N:3]([CH2:1][CH3:2])[C:8]=3[CH:9]=2)[CH:15]=1)(=[O:18])[CH3:30]

参加物

6

反応物 4

HCID 3283Diethyl EtherHCID 159087TriacetoxyperiodinaneHCID 866116753-(4-Ethyl-2,2,7-trimethyl-3-oxo-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4-trifluoromethoxy-benzaldehydeHCID 178418573HCID 178418573、化合物

生成物 1

HCID 685840906-(5-Acetyl-2-trifluoromethoxy-phenyl)-4-ethyl-2,2,7-trimethyl-4h-benzo[1,4]oxazin-3-one収率 46%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of Compound 1D (200 mg, 0.49 mmol) in dry 3 mL of dry THF is cooled to −78° C. and treated with a 3M solution of methyl magnesium bromide in diethyl ether (0.17 mL, 0.54 mmol). The reaction was allowed to warm to room temperature, the reaction turned blue when it was complete. The mixture was quenched with 5 mL of a saturated aqueous solution of NH4Cl and passed through a SPE. The crude product was eluted with EtOAc. After removing excess solvent the crude alcohol was then dissolved in 2 mL of dichloromethane and treated with Dess-Martin reagent (250 mg, 0.59 mmol) and stirred at room temperature overnight. The reaction was quenched with 4 mL of saturated sodium thiosulfate solution and 4 mL of saturated sodium bicarbonate solution, the reaction mixture was stirred until clear. The reaction mixture was passed through another SPE and eluted with dichloromethane, removal of solvent yielded crude ketone which was purified with flash chromatography (25% EtOAc/hexane) to yield 95 mg (46%) of the desired product and a white solid. MS (electrospray): mass calculated for C22H22F3NO4, 421.15; m/z found 422.1 [M+H]+.

後処理

  1. customThe mixture was quenched with 5 mL of a saturated aqueous solution of NH4Cl
  2. washThe crude product was eluted with EtOAc
  3. customAfter removing excess solvent the crude alcohol
  4. dissolutionwas then dissolved in 2 mL of dichloromethane
  5. customThe reaction was quenched with 4 mL of saturated sodium thiosulfate solution and 4 mL of saturated sodium bicarbonate solution
  6. stirringthe reaction mixture was stirred until clear
  7. washeluted with dichloromethane, removal of solvent
  8. customyielded crude ketone which
  9. customwas purified with flash chromatography (25% EtOAc/hexane)

出典と根拠

ORDレコード
ord-97869b4abf3b43cabbff1b07533ce392
出典データセット
uspto-grants-2010_05
特許番号
US07723326B2

反応ノート

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