2-Aminothiophenol → Benzo(d)thiazol-2-amine

HRID 2224642Notes

Reaction equation

HRID 2224642 reaction equation
[OH-].[Na+].[NH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[SH:10].CS[C:13](=[N:16]C1C=CC(C(N2C=CN=C2)C(C)N(C)C)=CC=1)SC.CSC(SC)NC1C=CC(C(N2C=NC=N2)C(CC)CC)=CC=1>CS(C)=O>[S:10]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:13]1[NH2:16]

Participants

6

Reactant 4

HCID 87132-AminothiophenolHCID 14798Sodium HydroxideHCID 22603047HCID 22603047, compoundHCID 22603060HCID 22603060, compound

Product 1

HCID 8706Benzo(d)thiazol-2-amine

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

NaOH (6.35 ml; 20 N) was added at RT to a solution of 2-aminobenzenethiol (0.0637 mol) in dimethylsulfoxide (115 ml). The mixture was stirred at RT for 30 minutes. (±)-β-[4[[bis(methylthio)methylene]amino]phenyl]-N,N,α-trimethyl-1H-imidazol-1-ethanamine (0.0637 mol), prepared according to intermediate (19a), was added. The mixture was stirred at 110° C. overnight, then poured out on ice, extracted with EtOAc and washed with HCl (3 N). The aqueous layer was basified with a concentrated NH4OH solution and extracted with EtOAc. The organic layer was separated, dried, filtered and the solvent was evaporated. The residue was separated by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 97/3/0.1 and 90/10/0.1). Two pure fractions (F1 and F2) were collected and their solvents were evaporate F1 was crystallized from 2-propanone. The precipitate was filtered off and dried. The residue was taken up in K2CO3 (10%), filtered and the solvent was evaporated, yielding 1.12 g (5%) (±)-(A)-N-[4-[2-dimethylamino)-1-(1H-imidazol-1-yl)propyl]phenyl]-2-benzothiazolamine (comp. 1). F2 was crystallized from 2-propanone. The precipitate was filtered off and dried. The residue was recrystallized from 2-propanone. The precipitate was filtered off and dried, yielding 0.9 g (4%) of (±)-(B)-N-[4-[2-dimethylamino)-1H-imidazol-1-yl)propyl]phenyl]-2-benzothiazolamine (comp. 2).

Workup

  1. additionwas added
  2. stirringThe mixture was stirred at 110° C. overnight
  3. additionpoured out on ice
  4. extractionextracted with EtOAc
  5. washwashed with HCl (3 N)
  6. extractionextracted with EtOAc
  7. customThe organic layer was separated
  8. customdried
  9. filtrationfiltered
  10. customthe solvent was evaporated
  11. customThe residue was separated by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 97/3/0.1 and 90/10/0.1)
  12. customTwo pure fractions (F1 and F2) were collected
  13. customtheir solvents were evaporate F1
  14. customwas crystallized from 2-propanone
  15. filtrationThe precipitate was filtered off
  16. customdried
  17. filtrationfiltered
  18. customthe solvent was evaporated

Sources & evidence

ORD record
ord-6ce56fa97b7d49ef9ee110dba82c1a14
Source dataset
uspto-grants-2008_05
Patent number
US07378433B2

Reaction notes

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