18-Crown-6 → Methyl 4-[1-{4-[2-(tert-butoxy)-1,1-difluoro-2-oxoethoxy]benzyl}-1-{4-[[di(tert-butoxy)phosphoryl](difluoro)methyl]benzyl}-2-(4-fluorophenyl)-2-oxoethyl]benzoate

HRID 1371019ノート

反応式

HRID 1371019 の反応式
[C:1]([O:5][C:6](=[O:38])[C:7]([F:37])([F:36])[O:8][C:9]1[CH:35]=[CH:34][C:12]([CH2:13][CH:14]([C:24]2[CH:33]=[CH:32][C:27]([C:28]([O:30][CH3:31])=[O:29])=[CH:26][CH:25]=2)[C:15]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)=[O:16])=[CH:11][CH:10]=1)([CH3:4])([CH3:3])[CH3:2].C1OCCOCCOCCOCCOCCOC1.CC(C)([O-])C.[K+].Br[CH2:64][C:65]1[CH:70]=[CH:69][C:68]([C:71]([P:74](=[O:85])([O:80][C:81]([CH3:84])([CH3:83])[CH3:82])[O:75][C:76]([CH3:79])([CH3:78])[CH3:77])([F:73])[F:72])=[CH:67][CH:66]=1>C1COCC1>[C:1]([O:5][C:6](=[O:38])[C:7]([F:36])([F:37])[O:8][C:9]1[CH:10]=[CH:11][C:12]([CH2:13][C:14]([C:24]2[CH:25]=[CH:26][C:27]([C:28]([O:30][CH3:31])=[O:29])=[CH:32][CH:33]=2)([CH2:64][C:65]2[CH:70]=[CH:69][C:68]([C:71]([P:74]([O:80][C:81]([CH3:84])([CH3:83])[CH3:82])([O:75][C:76]([CH3:77])([CH3:79])[CH3:78])=[O:85])([F:72])[F:73])=[CH:67][CH:66]=2)[C:15]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)=[O:16])=[CH:34][CH:35]=1)([CH3:4])([CH3:2])[CH3:3]

参加物

6

反応物 4

HCID 2855718-Crown-6HCID 15922636Di(tert-butyl) [4-(bromomethyl)phenyl](difluoro)methylphosphonateHCID 18510241Methyl 4-[1-{4-[2-(tert-butoxy)-1,1-difluoro-2-oxoethoxy]benzyl}-2-(4-fluorophenyl)-2-oxoethyl]benzoateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 18510258Methyl 4-[1-{4-[2-(tert-butoxy)-1,1-difluoro-2-oxoethoxy]benzyl}-1-{4-[[di(tert-butoxy)phosphoryl](difluoro)methyl]benzyl}-2-(4-fluorophenyl)-2-oxoethyl]benzoate収率 48.8%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of methyl 4-[1-{4-[2-(tert-butoxy)-1,1-difluoro-2-oxoethoxy]benzyl}-2-(4-fluorophenyl)-2-oxoethyl]benzoate (0.176 g, 0.333 mmol)) in degassed THF (1.7 ml), were added at −20° C. 18-crown-6 (0.15 g) and potassium tert-butoxide 1 M in THE (0.379 ml ). Di(tert-butyl) [4-(bromomethyl)phenyl](difluoro)methylphosphonate (0.156 g, 0.378 mmol) was then added and the reaction mixture was allowed to warm to room temperature. The reaction was quenched with saturated ammonium acetate solution and extracted with ethyl acetate. The organic phase was dried over sodium sulfate, filtered and evaporated to dryness. The residue was purified by flash chromatography using hexane/ethyl acetate 20% giving 0.140 g of the title compound.

後処理

  1. customThe reaction was quenched with saturated ammonium acetate solution
  2. extractionextracted with ethyl acetate
  3. dry with materialThe organic phase was dried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated to dryness
  6. customThe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-a3c05e608267479fad71a001cb8aa16a
出典データセット
uspto-grants-2003_06
特許番号
US06583126B2

反応ノート

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