Nitrogen → HCID 67958189, compound

HRID 527638Notes

Reaction equation

HRID 527638 reaction equation
N#N.[CH3:3][C:4]([Si:7]([CH3:21])([CH3:20])[O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH2:17][O:18][CH3:19])[CH:11]=1)([CH3:6])[CH3:5].C([Li])CCC.Cl[C:28]([O:30][CH2:31][CH3:32])=[O:29]>CCCCCC.O1CCCC1>[Si:7]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH2:17][O:18][CH3:19])[C:11]=1[C:28]([O:30][CH2:31][CH3:32])=[O:29])([C:4]([CH3:3])([CH3:5])[CH3:6])([CH3:20])[CH3:21]

Participants

7

Reactant 4

HCID 947NitrogenHCID 10928Ethyl chloroformateHCID 67958400HCID 67958400, compound2×HCID 178418339Butyllithium

Product 1

HCID 67958189HCID 67958189, compoundYield 74.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Procedure

Under nitrogen flush, in a 2-necked 100 ml round-bottomed flask equipped with a reflux condenser (flammed for 5 minutes under vacuum and then 3 cycles of N2/vacuum), (1,1-dimethylethyl)(dimethyl){[(3-{[(methyloxy)methyl]oxy}phenyl)methyl]oxy}silane (Intermediate 103, 1.5 g, 5.31 mmol) was dissolved in hexane (20 ml) to give a colourless solution. Butyllithium 1.6N in hexane (4.31 ml, 6.9 mmol) was added dropwise and the reaction mixture was stirred at room temperature. After 2 hours stirring in those conditions, the pale yellow reaction mixture was added to a solution of ethyl chloroformate (1.015 ml, 10.62 mmol) in tetrahydrofuran at −78° C. After 30 min, the reaction was quenched with a 2M aqueous solution of hydrochloric acid while the pH was allowed to reach ˜2 and diluted with 10 ml of ethyl acetate. Two phases were separated and the organic layer was dried over Na2SO4 and evaporated under vacuum affording the crude product as a yellowish oil that was purified by flash chromatography (Biotage system) on silica gel using cyclohexane to cyclohexane/ethyl acetate 8:2 as eluents affording the title compound (1.396 g) as a yellow pale oil.

Workup

  1. customUnder nitrogen flush, in a 2-necked 100 ml round-bottomed flask
  2. customequipped with a reflux condenser (
  3. customto give a colourless solution
  4. stirringAfter 2 hours stirring in those conditions
  5. waitAfter 30 min
  6. customthe reaction was quenched with a 2M aqueous solution of hydrochloric acid while the pH
  7. additiondiluted with 10 ml of ethyl acetate
  8. customTwo phases were separated
  9. dry with materialthe organic layer was dried over Na2SO4
  10. customevaporated under vacuum
  11. customaffording the crude product as a yellowish oil that
  12. customwas purified by flash chromatography (Biotage system) on silica gel

Sources & evidence

ORD record
ord-0f3fbce4464d47fd8ecd512e81cb4348
Source dataset
uspto-grants-2016_05
Patent number
US09346790B2

Reaction notes

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