Lawesson's reagent → HCID 86727311, compound

HRID 518962Notes

Reaction equation

HRID 518962 reaction equation
[CH2:1]([O:3][C:4](=[O:22])[CH:5]([N:7]1[C:12]2[CH:13]=[C:14]([N+:18]([O-:20])=[O:19])[C:15]([CH3:17])=[CH:16][C:11]=2[O:10][CH2:9][C:8]1=O)[CH3:6])[CH3:2].COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:32])=CC=1>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4](=[O:22])[CH:5]([N:7]1[C:12]2[CH:13]=[C:14]([N+:18]([O-:20])=[O:19])[C:15]([CH3:17])=[CH:16][C:11]=2[O:10][CH2:9][C:8]1=[S:32])[CH3:6])[CH3:2]

Participants

4

Reactant 2

HCID 87949Lawesson's reagentHCID 86727310HCID 86727310, compound

Product 1

HCID 86727311HCID 86727311, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 2-(7-methyl-6-nitro-3-oxo-2,3-dihydro-benzo[1,4]oxazin-4-yl)-propionic acid ethyl ester (0.5 g crude, 48% pure, 0.81 mmol) and Lawesson's reagent (0.656 g, 1.62 mmol) in toluene (30 mL) was heated at 120° C. for 20 h. The reaction mixture was cooled to ambient temperature and the solvent was removed in vacuo to give the crude product, which was purified by chromatography on silica gel (eluting with 20% EtOAc in petroleum ether) and further purified by preparative TLC (eluting with 20% EtOAc in petroleum ether) to give 2-(7-methyl-6-nitro-3-thioxo-2,3-dihydro-benzo[1,4]oxazin-4-yl)-propionic acid ethyl ester (0.130 g, 50%) as a solid. 1H NMR (CDCl3, 400 MHz): δ 7.64 (s, 1H), 6.90 (s, 1H), 6.61 (s, 1H), 4.90 (q, J=15.6 Hz, 2H), 4.20 (q, J=7.2 Hz, 2H), 2.54 (s, 3H), 1.65 (d, J=7.2 Hz, 3H), 1.21 (t, J=7.2 Hz, 3H).

Workup

  1. customthe solvent was removed in vacuo
  2. customto give the crude product, which
  3. customwas purified by chromatography on silica gel (eluting with 20% EtOAc in petroleum ether)
  4. customfurther purified by preparative TLC (eluting with 20% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-e78aecab9b444515a96740bb53c41730
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

Loading…