Ammonium Chloride → 7-Cyclopentyl-5-hydroxyspiro[chromen-2,1'-cyclobutan]-4(3H)-one

HRID 1516714ノート

反応式

HRID 1516714 の反応式
FC(F)(F)S(O[C:7]1[CH:19]=[C:18]2[C:10]([C:11](=[O:20])[CH2:12][C:13]3([O:17]2)[CH2:16][CH2:15][CH2:14]3)=[C:9]([OH:21])[CH:8]=1)(=O)=O.[Cl-].[Li+].[Br-].[CH:27]1([Zn+])[CH2:31][CH2:30][CH2:29][CH2:28]1.[Cl-].[NH4+]>O.Cl.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CN(C)C=O>[CH:27]1([C:7]2[CH:19]=[C:18]3[C:10]([C:11](=[O:20])[CH2:12][C:13]4([O:17]3)[CH2:16][CH2:15][CH2:14]4)=[C:9]([OH:21])[CH:8]=2)[CH2:31][CH2:30][CH2:29][CH2:28]1

参加物

10

反応物 4

HCID 25517Ammonium ChlorideHCID 433294Lithium ChlorideHCID 58002968HCID 58002968、化合物HCID 178419768HCID 178419768、化合物

生成物 1

HCID 580029377-Cyclopentyl-5-hydroxyspiro[chromen-2,1'-cyclobutan]-4(3H)-one

試薬・触媒・溶媒 5

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

Under argon, 8.45 g (24.0 mmol) of 5-hydroxy-4-oxo-3,4-dihydrospiro[chromen-2,1′-cyclobutan]-7-yl trifluoromethanesulfonate (Example 44A), 3.92 g (4.8 mmol) of [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(II) and 6.10 g (144.0 mmol) of lithium chloride are suspended in 250 ml of abs. dimethylformamide. The mixture is cooled to 0° C., 216 ml (108 mmol) of (cyclopentyl)zinc bromide (0.5 M solution in tetrahydrofuran) are added and the mixture is stirred at room temperature overnight. Saturated ammonium chloride solution is then added to the mixture. The mixture is diluted with water, 1 N hydrochloric acid and ethyl acetate, the organic phase is separated off and the aqueous phase is extracted repeatedly with ethyl actate. The combined organic phases are washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The residue is adsorbed on silica gel and purified on a silica gel column (mobile phase: cyclohexane→cyclohexane/ethyl acetate 10:1). This gives 6.2 g (94% of theory) of the title compound in a purity of 90%.

後処理

  1. customthe organic phase is separated off
  2. extractionthe aqueous phase is extracted repeatedly with ethyl actate
  3. washThe combined organic phases are washed twice with water and once with saturated sodium chloride solution
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified on a silica gel column (mobile phase: cyclohexane→cyclohexane/ethyl acetate 10:1)

出典と根拠

ORDレコード
ord-af04e7208a7f4ae9ab49990d13af7f1e
出典データセット
uspto-grants-2012_07
特許番号
US08227511B2

反応ノート

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