1-Acetoxy-2-bromoethane → HCID 23287579, compound

HRID 367214Notes

Reaction equation

HRID 367214 reaction equation
[H-].[Li+].[Cl:3][C:4]1[CH:21]=[CH:20][C:7]([NH:8][C:9]2[S:10][C:11]3[N:19]=[CH:18][CH:17]=[CH:16][C:12]=3[C:13](=[O:15])[N:14]=2)=[CH:6][CH:5]=1.[C:22]([O:25][CH2:26][CH2:27]Br)(=[O:24])[CH3:23]>CN(C=O)C>[Cl:3][C:4]1[CH:21]=[CH:20][C:7]([N:8]=[C:9]2[N:14]([CH2:23][C:22]([O:25][CH2:26][CH3:27])=[O:24])[C:13](=[O:15])[C:12]3[CH:16]=[CH:17][CH:18]=[N:19][C:11]=3[S:10]2)=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 135641-Acetoxy-2-bromoethaneHCID 62714Lithium hydrideHCID 42920704H-Pyrido[3,2-e]-1,3-thiazin-4-one, 2-[(4-chlorophenyl)amino]-2×

Product 1

HCID 23287579HCID 23287579, compoundYield 67.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

In an atmosphere of argon, a mixture of 34 mg (4.3 mmol) of lithium hydride and 5 ml of DMF was put in a 100 ml flask. To the flask was then connected a dropping funnel which contained 804 mg (2.8 mmol) of 2-(4-chloroanilino)-4H-pyrido[3,2-e]-1,3-thiazin-4-one and 10 ml of DMF. The solution of 2-(4-chloroanilino)-4H-pyrido[3,2-e]-1,3-thiazin-4-one was then added dropwise to the aforementioned mixture with stirring in 5 minutes. The mixture was further stirred for 50 minutes. To the mixture was then added a mixture of 704 mg of 2-bromoethyl acetate and 1 ml of DMF. The mixture was then stirred for 22 hours. After the termination of reaction, the mixture was concentrated under reduced pressure. The resulting residue was then extracted with water and ethyl acetate. The resulting organic phase was separated, washed with water and saturated brine, and then dried over sodium sulfate. The drying agent was then removed by filtration. The filtrate was then concentrated under reduced pressure. The resulting residue was then purified through silica gel column chromatography (eluant: 1/1 mixture of ethyl acetate and normal hexane). As a result, 708 mg of ethyl 2-[2-(4-chlorophenyl)imino-4-oxo-2,3-dihydro-4H-pyrido[3,2-e]-1,3-thiazin-3-yl]acetate was obtained as a low polarity substance, and 96 mg of ethyl 2-[N-(4-chlorophenyl)-N-(4-oxo-4H-pyrido[3,2-e]-1,3-thiazin-2-yl)amino]acetate was obtained as a high polarity substance. To a mixture of 89 mg of ethyl 2-[N-(4-chlorophenyl)-N-(4-oxo-4H-pyrido[3,2-e]-1,3-thiazin-2-yl)amino]acetate and 5 ml of ethanol was then added 14 mg of fumaric acid. The mixture was then stirred at room temperature for 1 hour. After the termination of reaction, the reaction was concentrated under reduced pressure, and then recrystallized from ethanol to obtain 104 mg of ethyl 2-[N-(4-chlorophenyl)-N-(4-oxo-4H-pyrido[3,2-e]-1,3-thiazin-2-yl)amino]acetate 0.5 fumarate.

Workup

  1. customwas put in a 100 ml flask
  2. stirringThe mixture was further stirred for 50 minutes
  3. additionTo the mixture was then added
  4. stirringThe mixture was then stirred for 22 hours
  5. customAfter the termination of reaction
  6. concentrationthe mixture was concentrated under reduced pressure
  7. extractionThe resulting residue was then extracted with water and ethyl acetate
  8. customThe resulting organic phase was separated
  9. washwashed with water and saturated brine
  10. dry with materialdried over sodium sulfate
  11. customThe drying agent was then removed by filtration
  12. concentrationThe filtrate was then concentrated under reduced pressure
  13. customThe resulting residue was then purified through silica gel column chromatography (eluant: 1/1 mixture of ethyl acetate and normal hexane)

Sources & evidence

ORD record
ord-e5a412ccc05c4b27a42c0c4190a9ead1
Source dataset
uspto-grants-2000_10
Patent number
US06133258

Reaction notes

Loading…