Pyridine → HCID 86736823, compound

HRID 1448938Notes

Reaction equation

HRID 1448938 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 mixtures 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 miutes 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. customat 0° C
  3. filtrationThe mixture is then filtered
  4. washthe celite cake is washed with methylene chloride (10×50 ml)
  5. washwashed with saturated sodium bicarbonate (2×150 ml)
  6. customThe methylene chloride phase is separated
  7. dry with materialdried (MgSO4)
  8. customthe solvents are removed at reduced pressure
  9. customThe crude product (1.3 g) is chromatographed on SilicAR CC-7 (25 g, Mallinckrodt) in hexane
  10. washElution with 7-10% ethyl acetate/hexane

Sources & evidence

ORD record
ord-5175db140b7e42048423c80734cf2e6c
Source dataset
uspto-grants-1980_02
Patent number
US04188328

Reaction notes

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