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

HRID 456930

반응식

HRID 456930 반응식
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]

참가 물질

7

반응물 5

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

생성물 1

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

시약·촉매·용매 1

HCID 702Ethanol용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-155202140dad4776b9b8eff48ddc033b
출처 데이터셋
uspto-grants-2007_03
특허 번호
US07186786B2

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