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

HRID 1109594Notes

Reaction equation

HRID 1109594 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-2c7c4617ef274f42a969e2406350e652
Source dataset
uspto-grants-1994_06
Patent number
US05321021

Reaction notes

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