Acetic Acid → HCID 21962576, compound

HRID 353039Notes

Reaction equation

HRID 353039 reaction equation
[CH2:1]([O:8][C:9]([N:11]([CH2:18][CH2:19][CH2:20][N:21]1[C:26]2[CH:27]=[CH:28][C:29]([S:31][CH:32]([C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[CH2:33][C:34]([O:36][CH2:37][CH3:38])=[O:35])=[CH:30][C:25]=2[O:24][CH2:23][C:22]1=[O:45])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br.C(O)(=[O:49])C>>[CH2:1]([O:8][C:9]([N:11]([CH2:18][CH2:19][CH2:20][N:21]1[C:26]2[CH:27]=[CH:28][C:29]([S:31][CH:32]([C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[CH2:33][C:34]([O:36][CH2:37][CH3:38])=[O:35])=[CH:30][C:25]=2[O:24][CH2:23][C:22]1=[O:45])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][N+:13]=1[O-:49])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 3

HCID 176Acetic Acid2×HCID 260Hydrogen BromideHCID 21962570HCID 21962570, compound

Product 1

HCID 21962576HCID 21962576, compound

Procedure

To a solution of titanium (IV) chloride in tetrahydrofuran under nitrogen atmosphere, is added and equimolar amount of stannous chloride dihydrate, and the mixture is stirred 1 hour at room temperature. Then, a solution of ethyl 3-[(4-{3-[N-benzyloxycarbonyl-N-(1-oxido-2-pyridinyl)amino]propyl}-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-7-yl)sulfanyl]-3-phenylpropanoate is added and the mixture heated 3 hours at 40° C. After evaporation of the solvent, ice and aqueous sodium bicarbonate are added, the mixture extracted with ethyl acetate, and the organic layers are combined and dried over sodium sulfate. The solvent is evaporated and ethyl 3-[(4-{3-[N-benzyloxycarbonyl-N-(2-pyridinyl)amino]-propyl}-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-7-yl)sulfanyl]-3-phenylpropanoate is isolated by column chromatography. A solution of ethyl 3-[(4-{3-[N-benzyloxycarbonyl-N-(2-pyridinyl)amino]-propyl)-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-7-yl)sulfanyl]-3-phenylpropanoate in acetic acid is treated with a solution of 30% hydrobromic acid in acetic acid at room temperature overnight. The solvent is evaporated under reduced pressure, and the residue is treated with a saturated sodium bicarbonate solution. The aqueous mixture is extracted with dichloromethane. The organic extracts are dried over sodium sulfate, evaporated to small volume and the product is purified by flash chromatography

Workup

  1. customThe solvent is evaporated under reduced pressure
  2. additionthe residue is treated with a saturated sodium bicarbonate solution
  3. extractionThe aqueous mixture is extracted with dichloromethane
  4. dry with materialThe organic extracts are dried over sodium sulfate
  5. customevaporated to small volume
  6. customthe product is purified by flash chromatography

Sources & evidence

ORD record
ord-d9722f2c100f4201afba44366acd4b95
Source dataset
uspto-grants-2004_06
Patent number
US06750215B2

Reaction notes

Loading…