Water → HCID 12044970, compound

HRID 412408Notes

Reaction equation

HRID 412408 reaction equation
[CH3:1][C:2]1([CH3:23])[C:7]2[CH:8]=[C:9]([C:12]3[N:16]([CH3:17])[C:15]([C:18]#[N:19])=[C:14](Br)[C:13]=3[CH3:21])[CH:10]=[CH:11][C:6]=2[NH:5][C:4](=[O:22])[O:3]1.[CH3:24][Sn](C)(C)C.O>CN(P(N(C)C)(N(C)C)=O)C>[CH3:1][C:2]1([CH3:23])[C:7]2[CH:8]=[C:9]([C:12]3[N:16]([CH3:17])[C:15]([C:18]#[N:19])=[C:14]([CH3:24])[C:13]=3[CH3:21])[CH:10]=[CH:11][C:6]=2[NH:5][C:4](=[O:22])[O:3]1

Participants

5

Reactant 3

HCID 962WaterHCID 11661TetramethyltinHCID 22260271HCID 22260271, compound

Product 1

HCID 12044970HCID 12044970, compoundYield 85.8%

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Procedure

A solution of 5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-3-bromo-1,4-dimethyl-1H-pyrrole-2-carbonitrile (0.11 g, 0.29 mmol), PhCNPdCl(PPh3)2 (cat., 11 mg) and tetramethyltin (10 eq, 0.53 g, 2.9 mmol) in HMPA (3 mL) was heated to 110° C. for 5d. The solution was allowed to cool, poured into water (20 mL) and extracted with ethyl acetate (3×15 mL). The combined organic layer was washed with brine, dried over MgSO4 and purified by flash column chromatography on silica gel eluting with 30% ethyl acetate/hexane to give 5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-1,3,4-trimethyl-1H-pyrrole-2-carbonitrile (77 mg, 85%) as a white solid. 1H NMR (300 MHz, d6-DMSO) δ 1.63 (s, 6H), 1.87 (s, 3H), 2.49 (s, 3H), 3.50 (s, 3H), 6.99 (d, 1H, J=8.2 Hz), 7.25 (dd, 1H, J=8.2, 1.4 Hz), 7.29 (s, 1H), 10.39 (s, 1H). MS (ESI (−)) 308 (M−H)−. Anal. calcd for C18H19N3O4, C, 69.9, H, 6.19, N, 13.6. Found, C, 68.8, H, 6.22, N, 12.9.

Workup

  1. temperatureto cool
  2. extractionextracted with ethyl acetate (3×15 mL)
  3. washThe combined organic layer was washed with brine
  4. dry with materialdried over MgSO4
  5. custompurified by flash column chromatography on silica gel eluting with 30% ethyl acetate/hexane

Sources & evidence

ORD record
ord-bda2e68cf4e44b7484fc39fd3ce300fb
Source dataset
uspto-grants-2003_05
Patent number
US06562857B2

Reaction notes

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