Triethylamine → HCID 87578542, compound

HRID 389015Notes

Reaction equation

HRID 389015 reaction equation
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[Si](O[CH2:27][C:28]1[C:29]([N+:40]([O-:42])=[O:41])=[C:30]([CH:37]=[CH:38][CH:39]=1)[C:31]([NH:33][CH2:34][C:35]#[CH:36])=[O:32])(C(C)(C)C)(C)C.C(N(CC)CC)C.[Br:50][C:51]([CH3:56])([CH3:55])[C:52](Br)=[O:53]>C1COCC1>[Br:50][C:51]([CH3:56])([CH3:55])[C:52]([CH2:27][C:28]1[C:29]([N+:40]([O-:42])=[O:41])=[C:30]([CH:37]=[CH:38][CH:39]=1)[C:31]([NH:33][CH2:34][C:35]#[CH:36])=[O:32])=[O:53]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 886852-Bromo-2-methylpropionyl bromideHCID 2724141Tetrabutylammonium FluorideHCID 57912296HCID 57912296, compound

Product 1

HCID 87578542HCID 87578542, compoundYield 62.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

TBAF (4.19 mL of a 1.0 M solution in THF) was added dropwise to a stirring solution of Compound 11 (487 mg, 1.40 mmol) in THF (14 mL). TLC analysis showed complete reaction after 5 minutes, after which time the THF was removed on a rotary evaporator and the resulting oil was dissolved in EtOAc (50 mL), washed with saturated NH4Cl (2×20 mL), water (2×50 mL), dried over MgSO4, concentrated in vacuo. The resulting white solid (Compound 12) was dissolved in anhydrous THF (14 mL), triethylamine (184 mg, 1.81 mmol) was added, and the resulting solution was added dropwise to a stirring solution of □-bromoisobutyrylbromide (225 mg, 1.82 mmol) in THF (5 mL) at 0° C. A white precipitate formed immediately. The mixture was allowed to warm to room temperature and stirred overnight under argon atmosphere after which time the solid salts were filtered, and the solvent was removed on a rotary evaporator. The resulting yellow oil was dissolved in ethyl acetate (50 mL) and washed with water (3×20 mL), dried over MgSO4, concentrated in vacuo, and purified by silica gel chromatography (50% EtOAc:hexanes) to yield Compound 13 (321 mg, 60%) as a white solid.

Workup

  1. customreaction after 5 minutes
  2. customafter which time the THF was removed on a rotary evaporator
  3. dissolutionthe resulting oil was dissolved in EtOAc (50 mL)
  4. washwashed with saturated NH4Cl (2×20 mL), water (2×50 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo
  7. dissolutionThe resulting white solid (Compound 12) was dissolved in anhydrous THF (14 mL)
  8. customA white precipitate formed immediately
  9. filtrationwere filtered
  10. customthe solvent was removed on a rotary evaporator
  11. dissolutionThe resulting yellow oil was dissolved in ethyl acetate (50 mL)
  12. washwashed with water (3×20 mL)
  13. dry with materialdried over MgSO4
  14. concentrationconcentrated in vacuo
  15. custompurified by silica gel chromatography (50% EtOAc:hexanes)

Sources & evidence

ORD record
ord-a0ff215ba35843e6a7c6b607b8b031db
Source dataset
uspto-grants-2013_02
Patent number
US08378041B2

Reaction notes

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