Sodium Carbonate → 1-methyl-5-(2-thioxo-1,2-dihydrospiro[3,1-benzoxazine-4,1'-cyclobutan]-6-yl)-1H-pyrrole-2-carbonitrile

HRID 458557Notes

Reaction equation

HRID 458557 reaction equation
[CH3:1][N:2]1[C:6]([C:7]2[CH:8]=[CH:9][C:10]3[NH:19][C:18](=O)[O:17][C:13]4([CH2:16][CH2:15][CH2:14]4)[C:11]=3[CH:12]=2)=[CH:5][CH:4]=[C:3]1[C:21]#[N:22].COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:32])=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1>[CH3:1][N:2]1[C:6]([C:7]2[CH:8]=[CH:9][C:10]3[NH:19][C:18](=[S:32])[O:17][C:13]4([CH2:16][CH2:15][CH2:14]4)[C:11]=3[CH:12]=2)=[CH:5][CH:4]=[C:3]1[C:21]#[N:22]

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 87949Lawesson's reagentHCID 113583221-methyl-5-(2-oxo-1,2-dihydrospiro [3,1-benzoxazine-4,1'-cyclobutan]-6-yl)-1H-pyrrole-2-carbonitrile

Product 1

HCID 104254421-methyl-5-(2-thioxo-1,2-dihydrospiro[3,1-benzoxazine-4,1'-cyclobutan]-6-yl)-1H-pyrrole-2-carbonitrileYield 99.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 1-methyl-5-(2-oxo-1,2-dihydrospiro[3,1-benzoxazine-4,1′-cyclobutan]-6-yl)-1H-pyrrole-2-carbonitrile (0.33 g, 1.1 mmol) and Lawesson's Reagent (0.23 g, 0.55 mmol) in toluene (10 mL) was heated at 100° C. Upon completion by TLC, the reaction mixture was poured into saturated sodium carbonate (100 mL) and extracted with ethyl acetate (50 mL), dried over magnesium sulfate, and concentrated. Trituration of the residue with ether (20 mL) gave 1-methyl-5-(2-thioxo-1,2-dihydrospiro[3,1-benzoxazine-4,1′-cyclobutan]-6-yl)-1H-pyrrole-2-carbonitrile (0.17 g, 49%) as a tan solid. 1H NMR (DMSO-d6): δ 12.35 (s, 1H), 7.64 (d, 1H, J=2.0 Hz), 7.51 (dd, 1H, J=8.2, 2.0 Hz), 7.15 (d, 1H, J=8.3 Hz), 7.05 (d, 1H, J=4.03 Hz), 6.43 (d, 1H, J=4.03 Hz), 3.73 (s, 3H), 2.59–2.53 (m, 2H), 2.09–2.02 (m, 2H), 1.93–1.85 (m, 2H). MS (ESI) m/z 310 ([M+H]+); MS (ESI) m/z 308 ([M−H]−); HRMS: calcd for C17H15N3OS, 309.0936; found (ESI_FT), 310.10057.

Workup

  1. extractionextracted with ethyl acetate (50 mL)
  2. dry with materialdried over magnesium sulfate
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-2b7aa1e571824338a5ddadb5b1cab1d0
Source dataset
uspto-grants-2007_03
Patent number
US07192956B2

Reaction notes

Loading…