Diethyl Ether → HCID 21187637, compound

HRID 549938Notes

Reaction equation

HRID 549938 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=1.[CH2:13]1[O:23][C:16]2([CH2:21][CH2:20][CH2:19][CH2:18][C:17]2=O)[O:15][CH2:14]1.CC[O:26]CC>O1CCCC1>[N:8]1[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=1[C:19]1([OH:26])[CH2:20][CH2:21][C:16]2([O:23][CH2:13][CH2:14][O:15]2)[CH2:17][CH2:18]1

Participants

6

Reactant 4

HCID 3283Diethyl Ether2×HCID 79732-BromopyridineHCID 123480741,4-Dioxaspiro[4.5]decan-6-oneHCID 178418339Butyllithium

Product 1

HCID 21187637HCID 21187637, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A mixture of n-butyllithium (1.6 M in hexanes, 8.8 ml) and anhydrous ether (20 ml) was stirred at −78° C. under argon and a solution of 2-bromopyridine (1.22 ml) in anhydrous ether (20 ml) added dropwise over 10 minutes. The resulting deep red solution was stirred for 10 minutes and a solution of cyclohexanedione monoethylene ketal (2 g) in tetrahydrofuran (20 ml) then introduced dropwise over 10 minutes. The resulting green suspension was maintained at −78° C. for one hour then warmed to −20° C. and stirred for a further hour, after which a yellow solution had formed. The reaction was quenched with saturated aqueous ammonium chloride (60 ml) and the layers separated. The aqueous was partitioned with dichloromethane (2×80 ml) and combined organics were dried (sodium sulphate) and concentrated in vacuo to give a yellow oil. This was adsorbed onto silica for purification by chromatography eluting with 0-100% ethyl acetate/isohexane to give 8-pyridin-2-yl-1,4-dioxaspiro[4.5]decan-8-ol as a pale yellow solid (1.45 g, 48%).

Workup

  1. stirringThe resulting deep red solution was stirred for 10 minutes
  2. temperatureThe resulting green suspension was maintained at −78° C. for one hour
  3. temperaturethen warmed to −20° C.
  4. stirringstirred for a further hour
  5. customafter which a yellow solution had formed
  6. customThe reaction was quenched with saturated aqueous ammonium chloride (60 ml)
  7. customthe layers separated
  8. customThe aqueous was partitioned with dichloromethane (2×80 ml)
  9. dry with materialcombined organics were dried (sodium sulphate)
  10. concentrationconcentrated in vacuo
  11. customto give a yellow oil
  12. customThis was adsorbed onto silica for purification by chromatography
  13. washeluting with 0-100% ethyl acetate/isohexane

Sources & evidence

ORD record
ord-e9575d47955e47b39630624bedc8aa91
Source dataset
uspto-grants-2011_05
Patent number
US07943768B2

Reaction notes

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