Tributylvinyltin → 1,1-Dibutyl-3-(1,1-dioxido-7-vinyl-4h-1,2,4-benzothiadiazin-3-yl)-6-fluoro-4-hydroxynaphthalen-2(1h)-one

HRID 2224815ノート

反応式

HRID 2224815 の反応式
[CH2:1]([C:5]1([CH2:31][CH2:32][CH2:33][CH3:34])[C:14]2[C:9](=[CH:10][C:11]([F:15])=[CH:12][CH:13]=2)[C:8]([OH:16])=[C:7]([C:17]2[NH:22][C:21]3[CH:23]=[CH:24][C:25](I)=[CH:26][C:20]=3[S:19](=[O:29])(=[O:28])[N:18]=2)[C:6]1=[O:30])[CH2:2][CH2:3][CH3:4].O1C=C[CH:37]=[C:36]1P(C1OC=CC=1)C1OC=CC=1.C([Sn](CCCC)(CCCC)CCCC)=C.[F-].[K+]>O1CCCC1.C(OCC)(=O)C>[CH2:1]([C:5]1([CH2:31][CH2:32][CH2:33][CH3:34])[C:14]2[C:9](=[CH:10][C:11]([F:15])=[CH:12][CH:13]=2)[C:8]([OH:16])=[C:7]([C:17]2[NH:22][C:21]3[CH:23]=[CH:24][C:25]([CH:36]=[CH2:37])=[CH:26][C:20]=3[S:19](=[O:29])(=[O:28])[N:18]=2)[C:6]1=[O:30])[CH2:2][CH2:3][CH3:4]

参加物

7

反応物 4

HCID 81998TributylvinyltinHCID 521585Tris(furan-2-yl)phosphaneHCID 522689Potassium FluorideHCID 1364037811,1-Dibutyl-6-fluoro-4-hydroxy-3-(7-iodo-1,1-dioxido-4h-1,2,4-benzothiadiazin-3-yl)naphthalen-2(1h)-one

生成物 1

HCID 1364036701,1-Dibutyl-3-(1,1-dioxido-7-vinyl-4h-1,2,4-benzothiadiazin-3-yl)-6-fluoro-4-hydroxynaphthalen-2(1h)-one収率 523.6%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
50 °C

実験手順

A solution of the compound of Example 20B (120 mg, 0.20 mmol), tri-(2-furyl)phosphine (5 mg, 0.020 mmol), tris-(dibenzylideneacetone)palladium (0) (9 mg, 0.010 mmol) in tetrahydrofuran (2 mL) was stirred at ambient temperature for 10 min, during which time the solution changed from a deep maroon color to pale green. The solution was treated with vinyltributylstannane (118 □L, 0.403 mmol) followed by warming at 50° C. for 1.5 h. The solution was cooled, diluted with ethyl acetate and stirred for 1 h with 1 M KF solution. The mixture was filtered through celite® and the layers separated. The organic layer was washed with saturated NaCl solution and dried over Na2SO4. Concentration in vacuo afforded an oil which was purified by flash chromatography eluting with ethyl acetate in hexane. These procedures afforded the title compound (52 mg, 52%) as a white solid. 1H NMR (300 MHz, CDCl3): δ 0.59 (m, 2 H) 0.73 (m, 6 H) 0.89 (m, 2 H) 1.15 (m, 4 H) 1.88 (m, 2 H) 2.31 (m, 2 H) 5.41 (d, J=11.03 Hz, 1 H) 5.85 (d, J=17.65 Hz, 1 H) 6.74 (dd, J=17.47, 10.85 Hz, 1 H) 7.30 (m, 2 H) 7.43 (m, 2 H) 7.68 (m, 1 H) 7.94 (m, 2 H) 16.80 (s, 1 H).

後処理

  1. temperatureThe solution was cooled
  2. filtrationThe mixture was filtered through celite®
  3. customthe layers separated
  4. washThe organic layer was washed with saturated NaCl solution
  5. dry with materialdried over Na2SO4
  6. concentrationConcentration in vacuo
  7. customafforded an oil which
  8. customwas purified by flash chromatography
  9. washeluting with ethyl acetate in hexane

出典と根拠

ORDレコード
ord-0801469346af452a94ed4aeb6a2f8e1c
出典データセット
uspto-grants-2008_05
特許番号
US07378414B2

反応ノート

読み込み中…