4-Bromophenyl isothiocyanate → (4-Bromo-phenyl)-(4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalen-6-yl)-amine

HRID 532575

Reaction equation

HRID 532575 reaction equation
[S:1]1[CH:5]=[CH:4][C:3]2[C:6](=O)[CH2:7][CH2:8][C:2]1=2.[Br:10][C:11]1[CH:16]=[CH:15][C:14]([N:17]=[C:18]=S)=[CH:13][CH:12]=1.C[Si](C)(C)[Si](C)(C)C.[Li].O.[NH2:30][NH2:31]>C1COCC1.O.C(O)(=O)C>[Br:10][C:11]1[CH:16]=[CH:15][C:14]([NH:17][C:18]2[C:7]3[CH2:8][C:2]4[S:1][CH:5]=[CH:4][C:3]=4[C:6]=3[NH:31][N:30]=2)=[CH:13][CH:12]=1

Participants

8

Reactant 4

HCID 161334-Bromophenyl isothiocyanateHCID 24654Hydrazine hydrate (1:1)HCID 19586324H,5H,6H-cyclopenta[b]thiophen-4-oneHCID 57425481Lithium hexamethyldisilane

Product 1

HCID 71815386(4-Bromo-phenyl)-(4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalen-6-yl)-amineYield 32%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 5,6-Dihydro-cyclopenta[b]thiophen-4-one (1.0 g, 7.4 mmol) and 1-Bromo-4-isothiocyanato-benzene (1.5 g, 7.2 mmol) in THF (2.0 mL) was added to lithium hexamethyl disilane (7.0 mL, 7.2 mmol) dropwise at room temperature. The reaction mixture was stirred for 8 hr. Hydrazine monohydrate (0.4 mL, 7.9 mmol) and glacial acetic acid (0.5 mL) were added to the reaction mixture, which was then heated at the reflux temperature for 24 hr. The resulting mixture was added to water (30 mL) and then extracted with ethyl acetate. The target product was purified by gravity column chromatography (50% EtOAc in hexane) to give (4-Bromo-phenyl)-(4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalen-6-yl)-amine as brown solid in 32% yield.

Workup

  1. temperaturewas then heated at the reflux temperature for 24 hr
  2. extractionextracted with ethyl acetate
  3. customThe target product was purified by gravity column chromatography (50% EtOAc in hexane)

Sources & evidence

ORD record
ord-b62f8fd057274d95b00d2f6fd690ce12
Source dataset
uspto-grants-2014_10
Patent number
US08853207B2

Linked notes

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