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

HRID 24298

反応式

HRID 24298 の反応式
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]

参加物

7

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

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, 3 H), δ=4.353 (s, 2 H), δ=4.47 (q, 2 H), δ=7.002 (t, 1 H), δ=7.234 (d, 1 H), δ=7.466 (t, 1 H), δ=8.377 (d, 1 H). 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).

後処理

  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

出典と根拠

ORDレコード
ord-518c9ea5171643dca04dc5c8b07f926a
出典データセット
uspto-grants-2005_02
特許番号
US06855840B2

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