((1,1-Dimethyl-2-propynyl)oxy)trimethylsilane → HCID 66643970, compound

HRID 655426Notes

Reaction equation

HRID 655426 reaction equation
[CH3:1][Si:2]([CH3:10])([CH3:9])[O:3][C:4]([CH3:8])([C:6]#[CH:7])[CH3:5].[Li]CCCC.[C:16]([C:18]1[CH:29]=[CH:28][C:21]([C:22](N(OC)C)=[O:23])=[CH:20][CH:19]=1)#[N:17]>C1COCC1>[CH3:5][C:4]([O:3][Si:2]([CH3:10])([CH3:9])[CH3:1])([CH3:8])[C:6]#[C:7][C:22]([C:21]1[CH:28]=[CH:29][C:18]([C:16]#[N:17])=[CH:19][CH:20]=1)=[O:23]

Participants

5

Reactant 3

HCID 87344((1,1-Dimethyl-2-propynyl)oxy)trimethylsilaneHCID 110196404-cyano-N-methoxy-N-methylbenzamideHCID 178418339Butyllithium

Product 1

HCID 66643970HCID 66643970, compoundYield 133.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a −78° C. stirred solution of trimethyl (2-methylbut-3-yn-2-yloxy)silane (3.3 g, 20.00 mmol) in dry THF (45 mL), n-BuLi (4.1 mL, 9.00 mmol, 1.6 M in hexane) was added dropwise over 10 minutes under an inert atmosphere. The reaction mixture was stirred for 30 min at −78° C., and then a solution of 4-cyano-N-methoxy-N-methylbenzamide (2.0 g, 10.00 mmol) in dry THF (15 mL) was added to the reaction mixture and stirring was continued for an additional 1 h at −78° C. The reaction mixture was quenched with a saturated NH4Cl solution and extracted with EtOAc (2×100 mL). The combined organic layers were washed with water (50 mL) and brine (50 mL), dried over Na2SO4, filtered, and concentrated in vacuo to obtain the crude product. The crude material was purified via silica gel column chromatography eluting with 15% EtOAc in hexanes to afford 4-(4-methyl-4-(trimethylsilyloxy) pent-2-ynoyl)benzonitrile (3.8 g, 68%) as a yellow oil.

Workup

  1. additionwas added dropwise over 10 minutes under an inert atmosphere
  2. stirringstirring
  3. waitwas continued for an additional 1 h at −78° C
  4. customThe reaction mixture was quenched with a saturated NH4Cl solution
  5. extractionextracted with EtOAc (2×100 mL)
  6. washThe combined organic layers were washed with water (50 mL) and brine (50 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto obtain the crude product
  11. customThe crude material was purified via silica gel column chromatography
  12. washeluting with 15% EtOAc in hexanes

Sources & evidence

ORD record
ord-4e99ca5350c640be93b5de51561edc02
Source dataset
uspto-grants-2011_12
Patent number
US08071595B2

Reaction notes

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