Diisopropylamine → HCID 59309385, compound

HRID 1690779Notes

Reaction equation

HRID 1690779 reaction equation
[CH:1]([O:4][C:5]1[CH:13]=[CH:12][C:11]([S:14]([CH3:17])(=[O:16])=[O:15])=[CH:10][C:6]=1[C:7]([OH:9])=[O:8])([CH3:3])[CH3:2].CN(CCN(C)C)C.[Li+].CC([N-]C(C)C)C.C([Li])CCC.C(NC(C)C)(C)C.I[CH2:47][Si:48]([CH3:51])([CH3:50])[CH3:49]>C1COCC1.CCCCCC>[CH:1]([O:4][C:5]1[CH:13]=[CH:12][C:11]([S:14]([CH2:17][CH2:47][Si:48]([CH3:51])([CH3:50])[CH3:49])(=[O:16])=[O:15])=[CH:10][C:6]=1[C:7]([OH:9])=[O:8])([CH3:3])[CH3:2]

Participants

9

Reactant 6

HCID 7912DiisopropylamineHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 77877(Iodomethyl)trimethylsilaneHCID 2724682Lithium diisopropylamideHCID 211002372-Isopropoxy-5-methylsulfonylbenzoic acidHCID 178418339Butyllithium

Product 1

HCID 59309385HCID 59309385, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

To a stirred −70° C. suspension of 0.26 g (1 mmol) 2-isopropoxy-5-methanesulfonyl-benzoic acid (CAS: 845616-02-6) and 0.75 ml (5 mmol) TMEDA in 2.6 ml THF was added dropwise a LDA solution (prepared from a 1.3 ml (2.1 mmol) 1.6M n-butyllithium solution in hexane and 0.3 ml (2.1 mmol) diisopropylamine in 2.5 ml THF at 0° C.). The light yellow suspension was stirred at −70° C. for 30 minutes. A solution of 0.19 ml (1.3 mmol) (iodomethyl)trimethylsilane in 0.5 ml THF was added dropwise over a period of 5 minutes. The yellow suspension was stirred at −70° C. for 15 minutes and then allowed to warm to room temperature. The light yellow solution was stirred at room temperature for 1 hour and then quenched with 5 ml brine. The mixture was diluted with 5 ml water. The mixture was concentrated in vacuo. The aqueous layer was carefully acidified with HCl 1N and extracted 3 times with dichloromethane. The combined extracts were dried over Na2SO4, filtered and concentrated in vacuo. The crude was purified with flash column chromatography on silica eluting with a gradient formed from heptane and ethylacetate to provide 0.21 g (63%) of the title compound as a yellow oil. MS (m/e): 343.0 [M−H]+.

Workup

  1. stirringThe yellow suspension was stirred at −70° C. for 15 minutes
  2. temperatureto warm to room temperature
  3. stirringThe light yellow solution was stirred at room temperature for 1 hour
  4. customquenched with 5 ml brine
  5. additionThe mixture was diluted with 5 ml water
  6. concentrationThe mixture was concentrated in vacuo
  7. extractionextracted 3 times with dichloromethane
  8. dry with materialThe combined extracts were dried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe crude was purified with flash column chromatography on silica eluting with a gradient
  12. customformed from heptane and ethylacetate

Sources & evidence

ORD record
ord-064fd5f116b541b0b1a6f2eeb53c38fb
Source dataset
uspto-grants-2012_04
Patent number
US08153679B2

Reaction notes

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