Oxygen → Carbonodithioic acid, O-ethyl S-(2-pyridinylmethyl) ester

HRID 349600

Reaction equation

HRID 349600 reaction equation
Br.Br[CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][N:5]=1.[CH2:10]([O:12][C:13](=[S:15])[SH:14])[CH3:11].[K].O=O.[OH-].[Na+]>C(O)C>[C:13]([S:15][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][N:5]=1)(=[S:14])[O:12][CH2:10][CH3:11]

Participants

7

Reactant 5

HCID 977OxygenHCID 8823Ethyl xanthateHCID 14798Sodium HydroxideHCID 27347202-(Bromomethyl)pyridine hydrobromideHCID 5462222Potassium

Product 1

HCID 85607002Carbonodithioic acid, O-ethyl S-(2-pyridinylmethyl) ester

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

1.00 g (3.9 mmol) of 2-(bromomethyl)pyridine hydrobromide and 0.36 g (3.9 mmol) of O-ethyldithiocarbonic acid, potassium salt were combined in a 50 ml round bottom flask with 20 ml of 100% ethanol. The reaction vessel was sealed with a rubber septum and oxygen was removed by several freeze-pump-thaw cycles. The reaction mixture was then warmed to room temperature and allowed to stir under positive nitrogen pressure. A white precipitate was observed after the first few minutes of the reaction. The reaction was allowed to stir for an additional 20 hours. 20 mL of 0.5M aqueous sodium hydroxide was then added causing the reaction mixture to become homogenous and take on a red color. Extraction with hexane after addition of an additional 20 ml of the sodium hydroxide solution yielded a fluorescent yellow-green solution. Hexane was removed and the residue was passed over a silica column (ethyl acetate as the elluent). The final product appears as a yellow-green liquid and fluoresces blue when exposed to long wavelength ultra-violet light. Yield=0.342 g (39%). 1H NMR (CDCl3) δ=1.212 (t, 3H), δ=4.353 (s, 2H), δ=4.47 (q, 2H), δ=7.002 (t, 1 H), δ=7.234 (d, 1H), δ=7.466 (t, 1H), δ=8.377 (d, 1H). 13C NMR (CDCl3) δ=13.929, δ=42.135, δ=70.358, δ=122.494 (CH), δ=123.424 (CH), δ=136.777 (CH), δ=149.660 (CH), δ=156.152 (C), δ=213.730 (C═S).

Workup

  1. customwas removed by several freeze-pump-thaw cycles
  2. customafter the first few minutes of the reaction
  3. stirringto stir for an additional 20 hours
  4. extractionExtraction with hexane
  5. additionafter addition of an additional 20 ml of the sodium hydroxide solution
  6. customyielded a fluorescent yellow-green solution
  7. customHexane was removed

Sources & evidence

ORD record
ord-820ee2b983ed45f0a9a3dd7856136089
Source dataset
uspto-grants-2007_02
Patent number
US07179872B2

Linked notes

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