Hydrochloric Acid → 2-(2,4-Dichloro-3-thienylamino)-1H-thieno[3,4-d]imidazole hydrochloride

HRID 349433Notes

Reaction equation

HRID 349433 reaction equation
C1(C)C=CC(S([Cl:10])(=O)=O)=CC=1.[NH2:12][C:13]1[C:14]([NH:18][C:19]([NH:21][C:22]2[C:26]([Cl:27])=[CH:25][S:24][C:23]=2[Cl:28])=S)=[CH:15][S:16][CH:17]=1.[OH-].[Na+].Cl>C1COCC1.O.C(OCC)(=O)C>[ClH:10].[Cl:28][C:23]1[S:24][CH:25]=[C:26]([Cl:27])[C:22]=1[NH:21][C:19]1[NH:18][C:14]2=[CH:15][S:16][CH:17]=[C:13]2[N:12]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 73974-Toluenesulfonyl chlorideHCID 14798Sodium HydroxideHCID 86037752N-(4-Amino-3-thienyl)-N'-(2,4-dichloro-3-thienyl)thiourea

Product 1

HCID 695138912-(2,4-Dichloro-3-thienylamino)-1H-thieno[3,4-d]imidazole hydrochloride

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 108.4 mg of p-toluenesulfonyl chloride in 5 ml of anhydrous THF was added dropwise to a mixture prepared from a solution of 157 mg of N-(4-amino-3-thienyl)-N′-(2,4-dichlorothienyl)thiourea in 15 ml of THF and a solution of 51.08 mg of NaOH in 2 ml of water. The resulting dark solution was stirred at room temperature for 2 hours, the solvent was distilled off and the residue was admixed with water. After extraction with ethyl acetate, the organic phase was washed with water and dried over sodium sulfate. After the solvent had been distilled off, the residue was purified by column chromatography on silica gel using a mixture of 20 parts by volume of ethyl acetate, 10 parts by volume of n-heptane, 3 parts by volume of glacial acetic acid as an eluent, which was then distilled off under reduced pressure. A viscous amorphous product was obtained which was dissolved in ethyl acetate and made strongly acidic using hydrogen chloride gas-saturated diethyl ether. The crystallization of the amorphous hydrochloric acid salt was brought about by scratching. M.p.: >300° C.

Workup

  1. distillationthe solvent was distilled off
  2. extractionAfter extraction with ethyl acetate
  3. washthe organic phase was washed with water
  4. dry with materialdried over sodium sulfate
  5. distillationAfter the solvent had been distilled off
  6. customthe residue was purified by column chromatography on silica gel using
  7. additiona mixture of 20 parts by volume of ethyl acetate, 10 parts by volume of n-heptane, 3 parts by volume of glacial acetic acid as an eluent
  8. distillationwhich was then distilled off under reduced pressure
  9. customA viscous amorphous product was obtained which
  10. customThe crystallization of the amorphous hydrochloric acid salt

Sources & evidence

ORD record
ord-981a9008d2944f699921517f681de425
Source dataset
uspto-grants-2007_02
Patent number
US07179830B2

Reaction notes

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