Potassium Carbonate → N-tert-butoxycarbonyl-amino-2-(5-nitro-2-pyridinylthio)ethane

HRID 731768Notes

Reaction equation

HRID 731768 reaction equation
[SH:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.[C:11]([O:15][C:16]([NH:18][CH2:19][CH2:20]Br)=[O:17])([CH3:14])([CH3:13])[CH3:12].C([O-])([O-])=O.[K+].[K+]>CC(C)=O>[C:11]([O:15][C:16]([NH:18][CH2:19][CH2:20][S:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1)=[O:17])([CH3:14])([CH3:13])[CH3:12]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 4103526tert-Butyl N-(2-bromoethyl)carbamateHCID 178526723C5H4N2O2S

Product 1

HCID 57838112N-tert-butoxycarbonyl-amino-2-(5-nitro-2-pyridinylthio)ethane

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A heterogeneous solution of 2-mercapto-5-nitropyridine (96 mg, 0.62 mmol), N-tert-butoxycarbonyl-amino-2-bromoethane (0.14 g, 0.63 mmol), and K2CO3 (0.42 g, 3.0 mmol) in acetone (10 mL) was heated at 60° C. for 15 h. The cooled reaction mixture was filtered through Celite®, concentrated, and then purified by silica gel chromatography to give N-tert-butoxycarbonyl-amino-2-(5-nitro-2-pyridinylthio)ethane (37), which was treated with trifluoroacetic acid (5 mL) in dichloromethane (5 mL) at room temperature for 30 min. The reaction mixture was concentrated and then residue was suspended in dichloromethane, washed with saturated NaHCO3 followed by brine, dried over anhydrous MgSO4 and concentrated to give 1-amino-2-[(5-nitro-2-pyridinyl)thio]ethane (38) as a tan solid which was used without further purification. 1H NMR (DMSO-d6): δ 9.21 (d, J=3.0 Hz, 1H), 8.41 (dd, J=2.4 and 8.7 Hz, 1H), 7.81 (bs, 2H), 7.65 (d, J=8.7 Hz, 1H), 3.44 (t, J=6.6 Hz, 2H), 3.12 (t, J=6.6 Hz, 2H).

Workup

  1. customThe cooled reaction mixture
  2. filtrationwas filtered through Celite®
  3. concentrationconcentrated
  4. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-41159dc253a84133bc8e69955fd26c35
Source dataset
uspto-grants-2009_09
Patent number
US07585883B2

Reaction notes

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