p-Toluenesulfonic acid → 4,5-dihydro-7-oxo-8-phenyl-7H-thieno[2,3-a]quinolizine-10-carboxaldehyde

HRID 477947Notes

Reaction equation

HRID 477947 reaction equation
[OH-].[OH:2][C:3]1[N+:7]2[CH2:8][CH2:9][C:10]3[CH:14]=[CH:13][S:12][C:11]=3[C:6]=2S[C:4]=1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C([O:23][CH:24](OCC)[C:25]#[CH:26])C.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(=O)CCCCC1>[O:2]=[C:3]1[C:4]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:26][C:25]([CH:24]=[O:23])=[C:6]2[N:7]1[CH2:8][CH2:9][C:10]1[CH:14]=[CH:13][S:12][C:11]=12

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 662853,3-DiethoxypropyneHCID 147700175,6-Dihydro-3-hydroxy-2-phenylthiazolo[3,2-a]thieno[2,3-c]pyridinium hydroxide

Product 1

HCID 147700384,5-dihydro-7-oxo-8-phenyl-7H-thieno[2,3-a]quinolizine-10-carboxaldehyde

Reagents, catalysts & solvents 1

HCID 7967CyclohexanoneSolvent

Procedure

A mixture of 0.855 g of 5,6-dihydro-3-hydroxy-2-phenylthiazolo[3,2-a]thieno[2,3-c]pyridinium hydroxide (internal salt) and 0.65 ml of 3,3-diethoxypropyne in 30 ml of cyclohexanone was stirred with a few crystals of p-toluenesulfonic acid at 130° for 3 hours under an inert gas and then concentrated in vacuo. The residue was taken up in ethyl acetate, washed with 10 percent potassium bicarbonate solution and saturated sodium chloride solution, dried over magnesium sulfate, concentrated and chromatographed on silica gel with toluene/acetonitrile (19:1). By crystallization from dioxane, there is obtained 4,5-dihydro-7-oxo-8-phenyl-7H-thieno[2,3-a]quinolizine-10-carboxaldehyde of m.p. 213°-215°.

Workup

  1. concentrationconcentrated in vacuo
  2. washwashed with 10 percent potassium bicarbonate solution and saturated sodium chloride solution
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. customchromatographed on silica gel with toluene/acetonitrile (19:1)
  6. customBy crystallization from dioxane

Sources & evidence

ORD record
ord-8be6b8cbf5d7432ca9387aa852481e50
Source dataset
uspto-grants-1989_12
Patent number
US04889848

Reaction notes

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