4-Aminopyridine → (10aS)-1,5,10,10a-Tetrahydro-3H-[1,3]thiazolo[3,4-b]isoquinoline-3-thione

HRID 461811Notes

Reaction equation

HRID 461811 reaction equation
[I-].C[S:3][C:4]1[S:5][CH2:6][C@@H:7]2[CH2:16][C:15]3[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=3[CH2:9][N+:8]=12.NC1C=CN=CC=1>N1C=CC=CC=1>[CH2:6]1[C@H:7]2[N:8]([CH2:9][C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:15]=3[CH2:16]2)[C:4](=[S:3])[S:5]1

Participants

4

Reactant 2

HCID 17274-AminopyridineHCID 12874874(S)-3-Methylthio-1,5,10,10a-tetrahydrothiazolo[3,4-b]isoquinolinium iodide

Product 1

HCID 54272298(10aS)-1,5,10,10a-Tetrahydro-3H-[1,3]thiazolo[3,4-b]isoquinoline-3-thioneYield 22.6%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

(S)-3-Methylthio-1,5,10,10a-tetrahydrothiazolo[3,4-b]isoquinolinium iodide (14.5 g.) is added, a little at a time, to a solution of 4-aminopyridine (7.5 g.) in pyridine (300 cc.). The suspension gradually passes into solution. After 24 hours at a temperature of about 20° C., the suspension is concentrated to dryness under reduced pressure (25 mm. Hg). The residue is dissolved in a mixture of methylene chloride (250 cc.) and water (200 cc.). The organic phase is decanted, dried over magnesium sulphate, filtered and then concentrated to about 100 cc. under reduced pressure. This solution is poured onto a column (column diameter: 3 cm) of silica gel (300 g.) and elution is then carried out with a 1% v/v solution of methanol in methylene chloride, eluate fractions of 500 cc. being collected. After evaporating fractions 2 and 3 to dryness, (S)-1,5,10,10a-tetrahydrothiazolo[3,4-b]isoquinoline-3-thione (2.0 g.) is obtained.

Workup

  1. concentrationthe suspension is concentrated to dryness under reduced pressure (25 mm. Hg)
  2. dissolutionThe residue is dissolved in a mixture of methylene chloride (250 cc.) and water (200 cc.)
  3. customThe organic phase is decanted
  4. dry with materialdried over magnesium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated to about 100 cc
  7. additionThis solution is poured onto a column (column diameter: 3 cm) of silica gel (300 g.) and elution
  8. custombeing collected
  9. customAfter evaporating fractions 2 and 3 to dryness

Sources & evidence

ORD record
ord-625936407c99403296ec3e2324b63f4f
Source dataset
uspto-grants-1977_12
Patent number
US04064247

Reaction notes

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