Triethylamine → 4-(3-Pyridinyl)-2-thiazolamine

HRID 1243670Notes

Reaction equation

HRID 1243670 reaction equation
[NH2:1][C:2]([NH:4][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=C[C:7]=1[N+:12]([O-])=O)=[S:3].Br.Br[CH2:17]C(C1C=NC=CC=1)=O.[NH4+].[Cl-].ClC(OC1C=CC([N+]([O-])=O)=CC=1)=O.CCN(CC)CC>CCO.[Fe].CO>[N:12]1[CH:9]=[CH:10][CH:11]=[C:6]([C:5]2[N:4]=[C:2]([NH2:1])[S:3][CH:17]=2)[CH:7]=1

Participants

9

Reactant 5

HCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 821294-Nitrophenyl chloroformateHCID 27762343-(2-Bromoacetyl)pyridine hydrobromideHCID 21928456Amino{[(2-nitrophenyl)methyl]amino}methane-1-thione

Product 1

HCID 1548934-(3-Pyridinyl)-2-thiazolamine

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 887MethanolSolvent

Procedure

[(2-Nitrophenyl)methyl](4-(3-pyridyl)(1,3-thiazol-2-yl)amine was prepared according to the method described in Example 16 (Step b) by employing amino{[(2-nitrophenyl)methyl]amino}methane-1-thione (1.03 g, 4.9 mmol) (Example 16, Step a), 3-(bromoacetyl)pyridine hydrobromide (Aust. J. Chem. 1989, 42, 1735; 1.37 g, 4.9 mmol), and 50% MeOH (50 mL). The crude yellow oil, iron dust (Aldrich) (1.39 g, 24.9 mmol) and NH4Cl (198 mg, 3.7 mmol) in 50% EtOH (50 mL) was heated at reflux. After 1 h the solvent was removed in vacuo. The residue was dissolved in THF (20 mL) and to this solution was added 4-nitrophenyl chloroformate (Aldrich) (860 mg, 4.2 mmol) followed by Et3N (0.85 mL, 6.1 mmol) and the reaction was heated at reflux. After 1 h the reaction was cooled to RT and stirred overnight. The solvent was removed in vacuo and purified by flash chromatography on silica gel with Hexanes:EtOAc (1:1) to CH2Cl2:MeOH (39:1, 19:1) as eluant to give an off-white solid. Mp: 269–272° C. MS m/z: 309 (M+1). Calc'd for C16H12N4OS—308.07.

Workup

  1. temperatureat reflux
  2. customAfter 1 h the solvent was removed in vacuo
  3. dissolutionThe residue was dissolved in THF (20 mL) and to this solution
  4. temperaturethe reaction was heated
  5. temperatureat reflux
  6. customThe solvent was removed in vacuo
  7. custompurified by flash chromatography on silica gel with Hexanes:EtOAc (1:1) to CH2Cl2:MeOH (39:1, 19:1) as eluant
  8. customto give an off-white solid

Sources & evidence

ORD record
ord-f6f2ed28f78d49cf8b86d650daedc84f
Source dataset
uspto-grants-2006_10
Patent number
US07119111B2

Reaction notes

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