4-Toluenesulfonyl chloride → HCID 54288902, compound

HRID 1904757Notes

Reaction equation

HRID 1904757 reaction equation
[NH:1]([C:5]1[C:13]2[C:8](=[C:9]([CH3:15])[N+:10]([O-])=[CH:11][CH:12]=2)[S:7][CH:6]=1)[C:2]([CH3:4])=[O:3].S(Cl)(C1C=CC(C)=CC=1)(=O)=O.[SH:27][C:28]1[NH:29][C:30]2[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=2[N:32]=1.C([O-])([O-])=O.[K+].[K+]>C1C=CC=CC=1.CN(C=O)C>[NH:1]([C:5]1[C:13]2[C:8](=[C:9]([CH2:15][S:27][C:28]3[NH:29][C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[N:32]=3)[N:10]=[CH:11][CH:12]=2)[S:7][CH:6]=1)[C:2]([CH3:4])=[O:3]

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 11430Potassium CarbonateHCID 53784470HCID 53784470, compoundHCID 178527775HCID 178527775, compound

Product 1

HCID 54288902HCID 54288902, compoundYield 26.8%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6228DimethylformamideSolvent

Procedure

To a refluxing solution of 202 mg (0.909 mmol) of 3-acetamino7-methylthieno[2, 3-c]pyridine N-oxide in anhydrous benzene was added 258 mg (1.5 equivalents) of TsCl, and the mixture was continued to be refluxed for 4 hr. After concentration under reduced pressure, the solution was subjected to silica gel column chromatography (silica gel : 30 g), eluting with CH2Cl2 : MeOH=20:1 v/v, whereby 3-acetamino-7-chloromethylthieno[2, 3-c]pyridine was separated. The produce was treated with 3 ml of anhydrous DMF, 136 mg (1 equivalent) of 2-mercaptobenzimidazole, and 502 mg (4 equivalents) of anhydrous K2CO3, and the mixture was stirred for 2.5 hr. at room temperature. After concentration under reduced pressure, the residue was extracted with ethyl acetate, and washed with water. The organic layer gave 237 mg of the crude crystals. The crystals were subjected to silica gel column chromatography (silica gel : 60 g), eluting with a solution of CH2Cl2 : MeOH=10:1 v/v, whereby 83 mg (Yield : 26.8%) of 2-[(3-acetaminothieno[2, 3-c]pyridin-7-yl]methylthio]benzimidazole (Ia-12) was obtained as an objective compound.

Workup

  1. temperatureto be refluxed for 4 hr
  2. concentrationAfter concentration under reduced pressure
  3. washeluting with CH2Cl2
  4. customMeOH=20:1 v/v, whereby 3-acetamino-7-chloromethylthieno[2, 3-c]pyridine was separated
  5. customat room temperature
  6. concentrationAfter concentration under reduced pressure
  7. extractionthe residue was extracted with ethyl acetate
  8. washwashed with water
  9. customThe organic layer gave 237 mg of the crude crystals
  10. washeluting with a solution of CH2Cl2

Sources & evidence

ORD record
ord-64674b5623f14405b16986f30ff4145b
Source dataset
uspto-grants-1989_06
Patent number
US04839365

Reaction notes

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