Diethyl Ether → HCID 57999483, compound

HRID 512011Notes

Reaction equation

HRID 512011 reaction equation
[CH3:1][N:2]1[NH:6][CH:5]=[CH:4]O1.[Li]CCCC.[Mg+2].[Br-].[Br-].CC[O:17]CC.[CH2:20]([O:27][C:28]1[CH:29]=[C:30]([C:34]2[CH:35]=[C:36]([CH:39]=[CH:40][CH:41]=2)[CH:37]=[O:38])[CH:31]=[CH:32][CH:33]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1COCC1.CCCCCC.[NH4+].[Cl-].CCOC(C)=O>[CH2:20]([O:27][C:28]1[CH:29]=[C:30]([C:34]2[CH:41]=[CH:40][CH:39]=[C:36]([CH:37]([C:1]3[O:17][C:5]([CH3:4])=[N:6][N:2]=3)[OH:38])[CH:35]=2)[CH:31]=[CH:32][CH:33]=1)[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1

Participants

10

Reactant 5

HCID 3283Diethyl EtherHCID 82241Magnesium BromideHCID 20099906HCID 20099906, compoundHCID 20213174HCID 20213174, compoundHCID 178418339Butyllithium

Product 1

HCID 57999483HCID 57999483, compoundYield 50%

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
-45 °C

Procedure

To a stirred solution of 63 (0.118 g, 1.5 mmol), in dry THF (5 mL), at −78° C., under a nitrogen atmosphere, was added n-BuLi (0.6 mL, 1.5 mmol, using a 2.5M solution in hexane) dropwise. Stirring continued for 10 min at −78° C. and then MgBr2.Et2O (0.4 g, 1.5 mmol) was added. The resulting mixture was warmed to −45° C. over a 2 hours period, and then it was cooled back to −78° C., and a solution of 76 (0.081 g, 0.28 mmol) in dry THF (5 mL) was added dropwise. Following the addition, the reaction mixture was warmed to −45° C. over a 2 hours period and then diluted with aqueous NH4Cl solution (5 mL) and AcOEt (20 mL). The resulting mixture was gradually warmed to room temperature, the organic phase was separated and the aqueous phase extracted with AcOEt. The combined organic layer was washed with brine, dried (MgSO4) and evaporated under reduced pressure. The residue obtained was purified by flash column chromatography on silica gel (75% ethyl acetate-hexane) to give 77 (0.052 g, 50% yield) as a colorless viscous liquid.

Workup

  1. temperatureit was cooled back to −78° C.
  2. additionthe addition
  3. temperaturethe reaction mixture was warmed to −45° C. over a 2 hours period
  4. temperatureThe resulting mixture was gradually warmed to room temperature
  5. customthe organic phase was separated
  6. extractionthe aqueous phase extracted with AcOEt
  7. washThe combined organic layer was washed with brine
  8. dry with materialdried (MgSO4)
  9. customevaporated under reduced pressure
  10. customThe residue obtained
  11. customwas purified by flash column chromatography on silica gel (75% ethyl acetate-hexane)

Sources & evidence

ORD record
ord-4f9d6ef10063431ba46b5ea676bdcae2
Source dataset
uspto-grants-2015_08
Patent number
US09102622B2

Reaction notes

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