Pyridine → 8-Methyl-1,4-dioxa-spiro[4,5]decane-8-carbaldehyde

HRID 1468209

Reaction equation

HRID 1468209 reaction equation
N1C=CC=CC=1.[CH3:7][C:8]1([CH2:18][OH:19])[CH2:17][CH2:16][C:11]2([O:15][CH2:14][CH2:13][O:12]2)[CH2:10][CH2:9]1>C(Cl)Cl.[O-2].[Cr+4].[O-2]>[CH3:7][C:8]1([CH:18]=[O:19])[CH2:17][CH2:16][C:11]2([O:12][CH2:13][CH2:14][O:15]2)[CH2:10][CH2:9]1

Participants

5

Reactant 2

HCID 1049PyridineHCID 12568263(8-Methyl-1,4-dioxaspiro[4.5]decan-8-yl)methanol

Product 1

HCID 575235548-Methyl-1,4-dioxa-spiro[4,5]decane-8-carbaldehydeYield 95.4%

Reagents, catalysts & solvents 2

HCID 73415796Chromium dioxideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Under a nitrogen atmosphere, solid chromium (IV) oxide (84.7 mmol, 8.47 g, 6.6 eq.) was added to a stirred solution of extra dry pyridine (171 mmol, 14.53 mL, 13.3 eq.) in dry methylene chloride (123 mL) cooled to 0° C. in an ice bath. The resulting solution was stirred at room temperature for 15 minutes. To this mixture was then added a solution of 4 (12.83 mmol, 2.28 g) in dry methylene chloride (19 mL) and the resulting mixture was stirred at room temperature for 30 minutes. The reaction mixture was then decanted into a seperatory funnel and the residue was washed with ethyl ether (40 mL and 50 mL). The washings were combined and the organic layer was washed with 5% aqueous sodium hydroxide solution (2×40 mL), 5% aqueous hydrochloric acid solution (3×40 mL), saturated aqueous sodium bicarbonate solution (3×40 mL) and brine (3×40 mL), then dried over magnesium sulfate, filtered, and concentrated in vacuo to give 5 (12.24 mmol, 2.35 g, 95%) as an amorphous solid. The product was used in the next reaction without further purification: 1H NMR (CDCl3) δ 9.47 (1H, s), 3.95 (4H, s), 2.00-1.96 (2H, m), 1.71-1.67 (2H, m), 1.61-1.53 (4H, m), 1.05 (s, 3H); 13C NMR (CDCl3) δ 205.9, 108.4, 64.4, 64.4, 45.7, 31.4, 29.9, 21.2.

Workup

  1. stirringthe resulting mixture was stirred at room temperature for 30 minutes
  2. customThe reaction mixture was then decanted into a seperatory funnel
  3. washthe residue was washed with ethyl ether (40 mL and 50 mL)
  4. washthe organic layer was washed with 5% aqueous sodium hydroxide solution (2×40 mL), 5% aqueous hydrochloric acid solution (3×40 mL), saturated aqueous sodium bicarbonate solution (3×40 mL) and brine (3×40 mL)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-afc105bcda024d88869ac1d1507c204e
Source dataset
uspto-grants-2015_04
Patent number
US09000188B2

Linked notes

Loading…