Lawesson's reagent → HCID 86727347, compound

HRID 518992Notes

Reaction equation

HRID 518992 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([O:12][C:13]2[CH:14]=[CH:15][C:16]3[O:21][CH2:20][C:19](=O)[N:18]([CH:23]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH3:24])[C:17]=3[CH:30]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:40])=CC=1>C1(C)C=CC=CC=1.COCCOC>[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([O:12][C:13]2[CH:14]=[CH:15][C:16]3[O:21][CH2:20][C:19](=[S:40])[N:18]([CH:23]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH3:24])[C:17]=3[CH:30]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 87949Lawesson's reagentHCID 86727345HCID 86727345, compound

Product 1

HCID 86727347HCID 86727347, compoundYield 74.5%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a solution of 3-[4-(1-ethoxycarbonyl-ethyl)-3-oxo-3,4-dihydro-2H-benzo[1,4]oxazin-6-yloxy]-azetidine-1-carboxylic acid tert-butyl ester (0.700 g, 1.66 mmol) in toluene (15 mL) and DME (15 mL) was added Lawesson's reagent (1.058 g, 2.66 mmol) and the mixture was heated to reflux for 4 h. The mixture was cooled to ambient temperature and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 15% EtOAc in petroleum ether) to give 3-[4-(1-ethoxycarbonyl-ethyl)-3-thioxo-3,4-dihydro-2H-benzo[1,4]oxazin-6-yloxy]-azetidine-1-carboxylic acid tert-butyl ester (0.540 g, 74%) as a white solid. 1H NMR (CDCl3, 400 MHz): δ 6.94 (d, J=8.8 Hz, 1H), 6.67 (br, 1H), 6.39 (m, 1H), 6.36 (m, 1H), 4.88 (d, J=15.2 Hz, 2H), 4.74 (m, 1H), 4.27 (m, 2H), 4.19 (m, 2H), 3.97 (m, 2H), 1.68 (d, J=7.2 Hz, 3H), 1.45 (s, 9H), 1.14 (t, J=7.2 Hz, 3H).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 4 h
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by column chromatography on silica gel (eluting with 15% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-aedd7565256947b88d78fd18e05ae116
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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