Pyridine → HCID 86736823, compound

HRID 127565Notes

Reaction equation

HRID 127565 reaction equation
N1C=CC=CC=1.[CH2:7]([O:14][CH:15]1[CH2:21][CH2:20][C:19]2([O:25][CH2:24][CH2:23][O:22]2)[CH2:18][O:17][C:16]1([CH3:33])[CH2:26][CH2:27][CH2:28][CH:29]([CH3:32])[CH2:30][OH:31])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1>C(Cl)Cl.[O-2].[O-2].[O-2].[Cr+6]>[CH2:7]([O:14][CH:15]1[CH2:21][CH2:20][C:19]2([O:22][CH2:23][CH2:24][O:25]2)[CH2:18][O:17][C:16]1([CH3:33])[CH2:26][CH2:27][CH2:28][CH:29]([CH3:32])[CH:30]=[O:31])[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

5

Reactant 2

HCID 1049PyridineHCID 20284848HCID 20284848, compound

Product 1

HCID 86736823HCID 86736823, compoundYield 83.1%

Reagents, catalysts & solvents 2

HCID 10219390chromium (VI) trioxideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

A solution of pyridine (3.6 g, 0.0444 mol) and chromium trioxide (2.2 g, 0.0222 mol) in methylene chloride (450 ml) at 23° C. in a nitrogen atmosphere is stirred for 45 minutes. The mixture is cooled to -10° C. and celite (13 g) is added followed by (2S*, 3R*)-3-benzyloxy-6,6-ethylenedioxy-2-methyl-2-(4'-methyl-5'-hydroxypentyl)-oxepane (1.4 g, 0.0037 mol) in methylene chloride (150 ml). The mixture is stirred for 1 hour at -10° C. and 30 minutes at 0° C. The mixture is then filtered and the celite cake is washed with methylene chloride (10×50 ml). The filtrate and washings are combined and washed with saturated sodium bicarbonate (2×150 ml). The methylene chloride phase is separated, dried (MgSO4) and the solvents are removed at reduced pressure. The crude product (1.3 g) is chromatographed on SilicAR CC-7 (25 g, Mallinckrodt) in hexane. Elution with 7-10% ethyl acetate/hexane gives (2S*, 3R*)-3-benzyloxy-6,6-ethylenedioxy-2-methyl-2-(4'-methyl-5'-oxopentyl)-oxepane as a clear colorless oil (1.157 g, 83%).

Workup

  1. additioncelite (13 g) is added
  2. filtrationThe mixture is then filtered
  3. washthe celite cake is washed with methylene chloride (10×50 ml)
  4. washwashed with saturated sodium bicarbonate (2×150 ml)
  5. customThe methylene chloride phase is separated
  6. dry with materialdried (MgSO4)
  7. customthe solvents are removed at reduced pressure
  8. customThe crude product (1.3 g) is chromatographed on SilicAR CC-7 (25 g, Mallinckrodt) in hexane
  9. washElution with 7-10% ethyl acetate/hexane

Sources & evidence

ORD record
ord-e01c3a056eb74a43b00372c510c5ac79
Source dataset
uspto-grants-1981_03
Patent number
US04256644

Reaction notes

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