Furan → 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)furan-2-carboxamide

HRID 906209

Reaction equation

HRID 906209 reaction equation
[CH3:1][C:2]1([CH3:14])[C:6]([CH3:8])([CH3:7])[O:5][B:4]([C:9]2[CH:13]=[CH:12][O:11][CH:10]=2)[O:3]1.ClS([N:19]=[C:20]=[O:21])(=O)=O.O1C=CC=C1>C(#N)C.O.C(Cl)Cl>[CH3:8][C:6]1([CH3:7])[C:2]([CH3:14])([CH3:1])[O:3][B:4]([C:9]2[CH:13]=[C:12]([C:20]([NH2:19])=[O:21])[O:11][CH:10]=2)[O:5]1

Participants

7

Reactant 3

HCID 8029FuranHCID 70918Chlorosulfonyl isocyanateHCID 27739962-(Furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 575899904-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)furan-2-carboxamideYield 49.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent2×HCID 6344DichloromethaneSolvent

Procedure

3-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)-furan (5.0 g, 25.77 mmol) is dissolved in dry acetonitrile (30 mL). Chlorosulfonylisocyanate (5.47 g, 38.65 mmol, 1.5 equiv.) in solution in dry acetonitrile (20 mL) is added in one portion at room temperature to the furan producing a pink solution that subsides overnight to turn yellow. The resulting solution is cooled with an ice bath and water (5 mL) is added, causing an exotherm. The resulting mixture is partitionned between DCM (100 mL) and water (30 mL). The aqueous layer is extracted 3 more times with DCM (50 mL), then the organic layers are gathered, washed with brine (10 mL), dried over anhydrous Na2SO4 and finally the solvent is removed under vacuum. The oily residue is dissolved in DCM (3 mL), sonicated to give a suspension of a crystalline solid. The solid is separated by filtration, and the cake is washed with a very small amount of DCM, then diethyl ether and dried under suction to afford 3 g of the title compound as a white powder.

Workup

  1. temperatureThe resulting solution is cooled with an ice bath
  2. extractionThe aqueous layer is extracted 3 more times with DCM (50 mL)
  3. washwashed with brine (10 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. customfinally the solvent is removed under vacuum
  6. dissolutionThe oily residue is dissolved in DCM (3 mL)
  7. customsonicated
  8. customto give
  9. additiona suspension of a crystalline solid
  10. customThe solid is separated by filtration
  11. washthe cake is washed with a very small amount of DCM
  12. dry with materialdiethyl ether and dried under suction

Sources & evidence

ORD record
ord-c973243a454c47948075c5d0123bb4ce
Source dataset
uspto-grants-2011_09
Patent number
US08012983B2

Linked notes

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