Tri-tert-butylphosphine tetrafluoroborate → HCID 56656346, compound

HRID 1778329Notes

Reaction equation

HRID 1778329 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:22]([C:23]([OH:25])=[O:24])=[C:21]2[C:16]([C:17]3[CH:29]=[CH:28][O:27][C:18]=3[C:19](=[O:26])[NH:20]2)=[CH:15][CH:14]=1)(=[O:11])=[O:10].[CH2:30]([N:32]([CH2:49][CH3:50])[CH2:33]/[CH:34]=[CH:35]\[Sn](CCCC)(CCCC)CCCC)[CH3:31].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:30]([N:32]([CH2:49][CH3:50])[CH2:33]/[CH:34]=[CH:35]\[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:22]([C:23]([OH:25])=[O:24])=[C:21]2[C:16]([C:17]3[CH:29]=[CH:28][O:27][C:18]=3[C:19](=[O:26])[NH:20]2)=[CH:15][CH:14]=1)(=[O:11])=[O:10])[CH3:31]

Participants

6

Reactant 3

HCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 66685610HCID 66685610, compound2×HCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine2×

Product 1

HCID 56656346HCID 56656346, compoundYield 30.6%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 7-(2-bromo-4-fluorobenzenesulfonylamino)-4-oxo-4,5-dihydrofuro[2,3-c]quinoline-6-carboxylic acid (Intermediate 86, 0.190 g), N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)-amine (Intermediate 3, 0.476 g), tris-(dibenzylideneacetone)dipalladium (0.043 g) and tri-tert-butylphosphonium tetrafluoroborate (0.023 g) in dioxane (5 mL) was heated under argon to 80° C. in a sealed vessel for 1 hour. The hot reaction mixture was filtered through Celite and washed with dioxane, ethyl acetate and acetonitrile. The filtrate was concentrated in vacuo and the residue was triturated with water and acetonitrile and then acetone. The solid was collected by filtration, dissolved in DMSO and filtered. The filtrate was purified by HPLC (C18) eluting with a mixture of acetonitrile and water, containing 0.1% formic acid, with a gradient of 25-75% acetonitrile, to give 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-4-oxo-4,5-dihydrofuro[2,3-c]quinoline-6-carboxylic acid (0.062 g).

Workup

  1. filtrationThe hot reaction mixture was filtered through Celite
  2. washwashed with dioxane, ethyl acetate and acetonitrile
  3. concentrationThe filtrate was concentrated in vacuo
  4. customthe residue was triturated with water and acetonitrile
  5. filtrationThe solid was collected by filtration
  6. dissolutiondissolved in DMSO
  7. filtrationfiltered
  8. customThe filtrate was purified by HPLC (C18)
  9. washeluting with a mixture of acetonitrile and water
  10. additioncontaining 0.1% formic acid

Sources & evidence

ORD record
ord-2a33880ead1340fdbc4f6e55d8d02d29
Source dataset
uspto-grants-2016_02
Patent number
US09266896B2

Reaction notes

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