Ethyl bromoacetate → HCID 22393123, compound

HRID 458523Notes

Reaction equation

HRID 458523 reaction equation
[O:1]=[S:2]1(=[O:28])[C:8]2[CH:9]=[C:10]([OH:15])[C:11]([S:13][CH3:14])=[CH:12][C:7]=2[N:6]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH2:5][C:4]([CH2:24][CH2:25][CH2:26][CH3:27])([CH2:22][CH3:23])[CH2:3]1.C(=O)([O-])[O-].[Na+].[Na+].Br[CH2:36][C:37]([O:39][CH2:40][CH3:41])=[O:38]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(=O)([O-])[O-].[Cs+].[Cs+].CC#N>[O:28]=[S:2]1(=[O:1])[C:8]2[CH:9]=[C:10]([O:15][CH2:36][C:37]([O:39][CH2:40][CH3:41])=[O:38])[C:11]([S:13][CH3:14])=[CH:12][C:7]=2[N:6]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH2:5][C:4]([CH2:24][CH2:25][CH2:26][CH3:27])([CH2:22][CH3:23])[CH2:3]1

Participants

7

Reactant 3

HCID 7748Ethyl bromoacetateHCID 10340Sodium CarbonateHCID 22393104HCID 22393104, compound

Product 1

HCID 22393123HCID 22393123, compoundYield 99%

Reagents, catalysts & solvents 3

HCID 10796Cesium carbonateCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

To 1,1-dioxo-3-butyl-3-ethyl-5-phenyl-7-methylthio-8-hydroxy-2,3,4,5-tetrahydro-1,5-benzothiazepine (Method 19; 500 mg, 1.2 mmol) was added MeCN (30 ml), tetrabutylammonium bromide (30 mg, 0.08 mmol), anhydrous sodium carbonate (500 mg, 4.7 mmol), ethyl bromoacetate (0.14 ml, 1.26 mmol) and caesium carbonate (20 mg, 0.06 mmol). This reaction mixture was then stirred over night at 80° C. Then the solvent was removed under reduced pressure, water and DCM were added and the aqueous phase was extracted three times with DCM. The combined organic phases were then dried, concentrated and purified by flash chromatography [DCM:EtOAc, 1:0, 9:1] to give the title compound 600 mg (99%). NMR (300 MHz) 0.8–1.0 (m, 6H), 1.0–1.8 (m, 11H), 2.2 (s, 3H), 3.2 (q, 2H) 3.75 (brq, 2H), 4.3 (q, 2H), 4.75 (s, 1H), 6.7 (s, 1H), 6.95 (t, 1H), 7.05 (d, 2H), 7.25 (t, 2H), 7.3 (s, 1H).

Workup

  1. customThen the solvent was removed under reduced pressure, water and DCM
  2. additionwere added
  3. extractionthe aqueous phase was extracted three times with DCM
  4. customThe combined organic phases were then dried
  5. concentrationconcentrated
  6. custompurified by flash chromatography [DCM:EtOAc, 1:0, 9:1]

Sources & evidence

ORD record
ord-4eec49078e7c42b096117737a483f215
Source dataset
uspto-grants-2007_03
Patent number
US07192946B2

Reaction notes

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