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 494494Notes

Reaction equation

HRID 494494 reaction equation
[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]

Participants

7

Reactant 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

Product 1

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

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-32c7a7243213401b82b32bbd40a5be66
Source dataset
uspto-grants-2009_05
Patent number
US07538105B2

Reaction notes

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