N,N,N',N'-Tetramethylethylenediamine → 1-(2-pyridyl)-1-[2,6-di(tetrahydro-2H-2-pyranyloxymethyl)phenyl]-methanol

HRID 1780920Notes

Reaction equation

HRID 1780920 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][O:16][CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][O:18]2)[C:10]=1Br.[Li]CCCC.CN(CCN(C)C)C.[CH:37]1[CH:42]=[C:41]([CH:43]=[O:44])[N:40]=[CH:39][CH:38]=1>CCOCC>[N:40]1[CH:39]=[CH:38][CH:37]=[CH:42][C:41]=1[CH:43]([C:10]1[C:9]([CH2:8][O:7][CH:2]2[CH2:3][CH2:4][CH2:5][CH2:6][O:1]2)=[CH:14][CH:13]=[CH:12][C:11]=1[CH2:15][O:16][CH:17]1[CH2:22][CH2:21][CH2:20][CH2:19][O:18]1)[OH:44]

Participants

6

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 142732-PyridinecarboxaldehydeHCID 190475892,6-di(tetrahydro-2H-2-pyranyloxymethyl)-phenyl bromideHCID 178418339Butyllithium

Product 1

HCID 100703421-(2-pyridyl)-1-[2,6-di(tetrahydro-2H-2-pyranyloxymethyl)phenyl]-methanolYield 73%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 2,6-di(tetrahydro-2H-2-pyranyloxymethyl)-phenyl bromide (15.5 g, 39 mmol) in ether at -30° C. was added n-BuLi (2.5M, 16.4 ml, 41 mmol) and the mixture was allowed to warm to room temperature and stirred for 1.5 hours. The mixture was cooled to 0° C., and TMEDA (4.56 g, 37 mmol) was added, and the resulting mixture was cooled to -50° C. After stirring for 20 minutes, 2-pyridylcarboxaldehyde (6.31 g , 58 mmol) was added. The above mixture was warmed to room temperature over a period of 2 hours, quenched with saturated sodium bicarbonate, and diluted with ethyl acetate with stirring. The organic layer was washed with brine and concentrated in vacuo to afford 11.7 g (73%) of 1-(2-pyridyl)-1-[2,6-di(tetrahydro-2H-2-pyranyloxymethyl)phenyl]-methanol as an oil.

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. temperaturethe resulting mixture was cooled to -50° C
  3. stirringAfter stirring for 20 minutes
  4. temperatureThe above mixture was warmed to room temperature over a period of 2 hours
  5. customquenched with saturated sodium bicarbonate
  6. additiondiluted with ethyl acetate
  7. stirringwith stirring
  8. washThe organic layer was washed with brine
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d817cdb898dc4c4791fd3470bd46b871
Source dataset
uspto-grants-1997_05
Patent number
US05631264

Reaction notes

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