Ethyl Acetate → N-(6-Bromo-5',6'-dihydro-4'H-spiro[chromene-2,3'-pyran]-4(3H)-ylidene)-2-methylpropane-2-sulfinamide

HRID 539354

反応式

HRID 539354 の反応式
[Br:1][C:2]1[CH:3]=[C:4]2[C:14](=[CH:15][CH:16]=1)[O:13][C:7]1([CH2:12][CH2:11][CH2:10][O:9][CH2:8]1)[CH2:6][C:5]2=O.[CH3:18][C:19]([S:22]([NH2:24])=[O:23])([CH3:21])[CH3:20].CCOC(C)=O.C([O-])(O)=O.[Na+]>CN1C2C(N=C(N)NC=2NCC1CNC1C=CC(C(NC(C(O)=O)CCC(O)=O)=O)=CC=1)=O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Br:1][C:2]1[CH:3]=[C:4]2[C:14](=[CH:15][CH:16]=1)[O:13][C:7]1([CH2:12][CH2:11][CH2:10][O:9][CH2:8]1)[CH2:6][C:5]2=[N:24][S:22]([C:19]([CH3:21])([CH3:20])[CH3:18])=[O:23]

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 516892Sodium BicarbonateHCID 3382465Tert-ButanesulfinamideHCID 584238236-Bromo-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-one2 回

生成物 1

HCID 67979337N-(6-Bromo-5',6'-dihydro-4'H-spiro[chromene-2,3'-pyran]-4(3H)-ylidene)-2-methylpropane-2-sulfinamide収率 97%

試薬・触媒・溶媒 2

HCID 76524Titanium tetraethoxide触媒HCID 178479889HCID 178479889、化合物溶媒

実験手順

6-Bromo-5′,6′-dihydro-4′H-spiro[chromene-2,3′-pyran]-4(3H)-one (Intermediate 26, 2.007 g, 6.75 mmol), 2-methylpropane-2-sulfinamide (1.228 g, 10.13 mmol) and titanium ethoxide (2.78 mL, 13.51 mmol) were dissolved in methyl THF (16 mL) and heated to reflux for 19 h. The reaction was left to cool down to r.t. when EtOAc (80 mL) and NaHCO3 (sat., 5 mL) were added under stirring. The mixture was let standing for 1 h. The organic phase was collected by filtration, dried over MgSO4 and concentrated. The crude product was purified by flash chromatography using a gradient of 0-50% EtOAc in heptane. The desired fractions were evaporated to give the title compound as a mixture of diastereomers in a ratio 1:1 as determined by NMR (2.63 g, 97% yield): 1H NMR (500 MHz, CDCl3) δ ppm 1.34 (s, 9H), 1.50-1.57 (m, 0.5H), 1.60-1.68 (m, 1H), 1.73 (m, 0.5H) 1.87-2.09 (m, 2H), 2.99 (d, 0.5H), 3.26 (d, 0.5H), 3.33 (d, 0.5H), 3.45-3.61 (m, 2H), 3.64 (d, 0.5H), 3.77-3.93 (m, 2H), 6.88-6.93 (m, 1H), 7.48 (dd, 1H), 7.98 (dd, 1H); MS (ES+) m/z 401.9 [M+H]+.

後処理

  1. temperatureheated
  2. temperatureto reflux for 19 h
  3. waitThe reaction was left
  4. additionwere added
  5. filtrationThe organic phase was collected by filtration
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customThe crude product was purified by flash chromatography
  9. customThe desired fractions were evaporated

出典と根拠

ORDレコード
ord-9e093ea93e9c489a96d5ca3e47b79ab5
出典データセット
uspto-grants-2014_10
特許番号
US08865911B2

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