Acetic Acid → HCID 21853906, compound

HRID 2072316Notes

Reaction equation

HRID 2072316 reaction equation
[C:1]([O:4][C:5]1[C:14]2[C:13]3[CH2:15][CH:16]([CH3:19])[CH2:17][CH2:18][C:12]=3[C:11]([CH3:21])([CH3:20])[O:10][C:9]=2[CH:8]=[C:7]([CH3:22])[CH:6]=1)(=[O:3])[CH3:2].C(Cl)(Cl)Cl.C(O)(=[O:29])C>>[C:1]([O:4][C:5]1[C:14]2[C:13]3[CH2:15][CH:16]([CH3:19])[CH2:17][C:18](=[O:29])[C:12]=3[C:11]([CH3:21])([CH3:20])[O:10][C:9]=2[CH:8]=[C:7]([CH3:22])[CH:6]=1)(=[O:3])[CH3:2]

Participants

4

Reactant 3

HCID 176Acetic Acid2×HCID 6212ChloroformHCID 50137Pirnabine

Product 1

HCID 21853906HCID 21853906, compoundYield 14.2%

Procedure

To a stirring mixture of 1-acetoxy-7,8,9,10-tetrahydro-3,6,6,9-tetramethyl-6H-dibenzo[ b,d]pyran (601 mg., 2 mmole) in 7 ml. of 50% acetic acid and 5 ml. of chloroform held under a nitrogen atmosphere, was added dropwise a solution of ceric ammonium nitrate (4.39 g., 8 mmole) in 12 ml. of 50% acetic acid. After the addition was completed, the reaction mixture was stirred over a steam bath. After 3 hours, the mixture was poured onto ice with stirring. The product was extracted into ether, washed to neutrality with 5% NaHCO3, washed with water, dried over Na2SO4 and concentrated under reduced pressure. Elution of the product from a mganesium silicate column with graded ether/petroleum ether gave 120 mg. (14.2%) of the desired product which showed a blue fluorescent spot on tlc at Rf 0.67 (silica gel, 40% EtOAc/hexane). Ir(neat) 1770(m), 1740(s), 1660(s), 1640(s), 1620(m) CM-1 ; nmr (CDCl3) δ 1.08(d,3H, J=4Hz), 1.38(S,3H), 1.7(S,3H), 2.3(S,6H), 1.0-3.0(broad m,5H), 6.5(S,1H), 6.62(S,1H).

Workup

  1. additionAfter the addition
  2. additionthe mixture was poured onto ice
  3. stirringwith stirring
  4. extractionThe product was extracted into ether
  5. washwashed
  6. washwashed with water
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. washElution of the product from a mganesium silicate column with graded ether/petroleum ether
  10. customgave 120 mg

Sources & evidence

ORD record
ord-301c25aede794971af95e50b9638b293
Source dataset
uspto-grants-1977_09
Patent number
US04051152

Reaction notes

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