Triethylamine → HCID 69275106, compound

HRID 844384Notes

Reaction equation

HRID 844384 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C@@H:9]2[C@H:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C@@H:12]([C:19]3[CH:27]=[CH:26][C:22]4[O:23][CH2:24][O:25][C:21]=4[CH:20]=3)[CH2:11][N:10]2[CH2:28][C:29]([N:31]([CH2:37][CH2:38][CH2:39][CH3:40])[CH2:32][CH2:33][CH2:34][CH2:35]O)=[O:30])=[CH:5][CH:4]=1.C(N(CC)CC)C.CS(Cl)(=O)=O.[Li+].[Br-:54]>C(OCC)C.CN(C=O)C.O>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C@@H:9]2[C@H:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C@@H:12]([C:19]3[CH:27]=[CH:26][C:22]4[O:23][CH2:24][O:25][C:21]=4[CH:20]=3)[CH2:11][N:10]2[CH2:28][C:29]([N:31]([CH2:37][CH2:38][CH2:39][CH3:40])[CH2:32][CH2:33][CH2:34][CH2:35][Br:54])=[O:30])=[CH:5][CH:4]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 82050Lithium BromideHCID 57187888HCID 57187888, compound

Product 1

HCID 69275106HCID 69275106, compoundYield 90%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To an ice cooled solution of 2.80 g (5.05 mmol) of the compound of Example 547C in 27 mL of diethyl ether was added 1.4 mL (10 mmol) of triethylamine, then 0.58 mL of methanesulfonyl chloride. A white precipitate formed, and the suspension was stirred at 0° C. for 20 min. The reaction was diluted with 75 mL of diethyl ether, then extracted with saturated aqueous NaHCO3 solution (2×25 mL), 5% NH4OH (2×25 mL), and brine (1×25 mL), dried over MgSO4, filtered, and concentrated to 3.0 g of a colorless oil. To this material in 45 mL of DMF was added 6.0 g (69 mmol) of LiBr. The reaction warmed to about 50° C., then gradually cooled. The solution was stirred at ambient temperature for 4 h, then poured into 450 mL of water, and extracted with diethyl ether (3×100 mL). The combined ether layers were back extracted with water (1×100 mL), and brine (1×100 mL), dried over MgSO4, filtered, and concentrated in vacuo to an oil. The product was purified via silica gel chromatography, eluting with 3:1 diethyl ether: petroleum ether, to give 2.65 g (90%) of a colorless oil.

Workup

  1. customA white precipitate formed
  2. extractionextracted with saturated aqueous NaHCO3 solution (2×25 mL), 5% NH4OH (2×25 mL), and brine (1×25 mL)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated to 3.0 g of a colorless oil
  6. temperatureThe reaction warmed to about 50° C.
  7. temperaturegradually cooled
  8. stirringThe solution was stirred at ambient temperature for 4 h
  9. extractionextracted with diethyl ether (3×100 mL)
  10. extractionThe combined ether layers were back extracted with water (1×100 mL), and brine (1×100 mL)
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo to an oil
  14. customThe product was purified via silica gel chromatography
  15. washeluting with 3:1 diethyl ether

Sources & evidence

ORD record
ord-ab46b573f73d409eb89532e9ca64fbfa
Source dataset
uspto-grants-2002_04
Patent number
US06380241B1

Reaction notes

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