Sodium Carbonate → N-(3-Xanthen-9-ylidenemethyl-phenyl)-methanesulfonamide

HRID 1454923Notes

Reaction equation

HRID 1454923 reaction equation
Br[CH:2]=[C:3]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[O:10][C:9]2[C:4]1=[CH:5][CH:6]=[CH:7][CH:8]=2.CC1(C)C(C)(C)OB([C:25]2[CH:26]=[C:27]([NH:31][S:32]([CH3:35])(=[O:34])=[O:33])[CH:28]=[CH:29][CH:30]=2)O1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:15]1[C:16]2[C:3](=[CH:2][C:25]3[CH:26]=[C:27]([NH:31][S:32]([CH3:35])(=[O:33])=[O:34])[CH:28]=[CH:29][CH:30]=3)[C:4]3[C:9](=[CH:8][CH:7]=[CH:6][CH:5]=3)[O:10][C:11]=2[CH:12]=[CH:13][CH:14]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 162177153-(Methanesulfonylamino)phenylboronic acid pinacol esterHCID 575312149-Bromomethylene-9H-xanthene

Product 1

HCID 57531196N-(3-Xanthen-9-ylidenemethyl-phenyl)-methanesulfonamideYield 3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

Mix 9-Bromomethylene-9H-xanthene (400 mg, 1.46 mmol), N-[3-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-methanesulfonamide (413 mg, 1.39 mmol), and Na2CO3 (2M/water, 1.74 mL, 3.48 mmol) in dioxane (10 mL) and sparge with nitrogen for 10 min. Add Pd(PPh3)4 (81 mg, 0.070 mmol), seal vial, and heat to 95° C. overnight. Concentrate and dilute with water (3 mL) and ethyl acetate (10 mL). Load mixture onto a Varian ChemElut CE1005 solid-phase extraction cartridge. Elute, collect, and concentrate 50 mL ethyl acetate. Purify on silica gel (20-40% ethyl acetate/hexanes), then re-purify by semi-prep reverse-phase HPLC (10-95% CH3CN/H2O, 0.1% TFA added) to afford 14 mg (3%) of the title compound as a yellow solid. MS [ES] 364 (M+H), 362 (M−H); HPLC shows 97% purity; 1H-NMR (CDCl3) δ 7.78 (d, 1H, J=7.5 Hz), 7.39-7.14 (m, 10H), 6.91 (s, 1H), 6.85 (t, 1H, J=7.5 Hz), 6.53 (s, 1H), 3.01 (s, 3H).

Workup

  1. customsparge with nitrogen for 10 min
  2. concentrationConcentrate
  3. additiondilute with water (3 mL) and ethyl acetate (10 mL)
  4. extractionLoad mixture onto a Varian ChemElut CE1005 solid-phase extraction cartridge
  5. washElute
  6. customcollect
  7. concentrationconcentrate 50 mL ethyl acetate
  8. customPurify on silica gel (20-40% ethyl acetate/hexanes)
  9. customre-purify by semi-prep reverse-phase HPLC (10-95% CH3CN/H2O, 0.1% TFA added)

Sources & evidence

ORD record
ord-7b43f01f11fc4fbc8df74b7aa54a1e0d
Source dataset
uspto-grants-2009_01
Patent number
US07482344B2

Reaction notes

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