Triethylamine → 7-((1-allylcyclopropyl)sulfonyl)-4-fluoro-5-(2-chloro-4-bromophenyl)-5H-imidazo[4',5':4,5]benzo[1,2-d]oxazol-6(7H)-one

HRID 928985Notes

Reaction equation

HRID 928985 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:19]3[C:11](=[CH:12][C:13]4[O:17][CH:16]=[N:15][C:14]=4[C:18]=3[F:20])[NH:10][C:9]2=[O:21])=[C:4]([Cl:22])[CH:3]=1.C(N(CC)CC)C.[CH2:30]([C:33]1([S:36](Cl)(=[O:38])=[O:37])[CH2:35][CH2:34]1)[CH:31]=[CH2:32].C([O-])(O)=O.[Na+]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH2:30]([C:33]1([S:36]([N:10]2[C:11]3=[CH:12][C:13]4[O:17][CH:16]=[N:15][C:14]=4[C:18]([F:20])=[C:19]3[N:8]([C:5]3[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][C:4]=3[Cl:22])[C:9]2=[O:21])(=[O:38])=[O:37])[CH2:35][CH2:34]1)[CH:31]=[CH2:32]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 516892Sodium BicarbonateHCID 441819591-(Prop-2-en-1-yl)cyclopropane-1-sulfonyl chlorideHCID 897053695-(4-bromo-2-chlorophenyl)-4-fluoro-5H-imidazo[4',5':4,5]benzo[1,2-d]oxazol-6(7H)-one

Product 1

HCID 897054527-((1-allylcyclopropyl)sulfonyl)-4-fluoro-5-(2-chloro-4-bromophenyl)-5H-imidazo[4',5':4,5]benzo[1,2-d]oxazol-6(7H)-oneYield 87.6%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 5-(4-bromo-2-chlorophenyl)-4-fluoro-5H-imidazo[4′,5′:4,5]benzo[1,2-d]oxazol-6(7H)-one (100 mg, 0.26 mmol) in DCM (10 mL) was added triethylamine (80 mg, 0.78 mmol) at 0° C. followed by 1-allylcyclopropane-1-sulfonyl chloride (71 mg, 0.39 mmol) and DMAP (15 mg). After stirring at room temperature for 1 h, the reaction was treated with saturated NaHCO3 (aq.). The aqueous layer was extracted with CH2Cl2 (20 mL×2). The combined organic phase was washed with water (20 mL) and brine (20 mL) sequentially, dried over Na2SO4, filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate, 5:1, v/v) to give the corresponding product (120 mg, 87.2% yield). 1H NMR (400 MHz, CDCl3): δ 8.09 (s, 1H), 7.99 (s, 1H), 7.39-7.11 (d, 2H), 7.05, (m, 1H), 5.75-5.58 (m, 1H), 5.05 (m, 2H), 2.90-2.80 (m, 1H), 2.10-2.0 (m, 1H), 1.95-1.86 (m, 2H), 1.25-1.10 (m, 2H).

Workup

  1. extractionThe aqueous layer was extracted with CH2Cl2 (20 mL×2)
  2. washThe combined organic phase was washed with water (20 mL) and brine (20 mL) sequentially
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a residue, which
  7. customwas purified by flash chromatography on silica gel (petroleum ether/ethyl acetate, 5:1

Sources & evidence

ORD record
ord-aa0c07aad4ae464bbca7d9841cf867d2
Source dataset
uspto-grants-2016_03
Patent number
US09290468B2

Reaction notes

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