Triethylamine → 4-(5-Bromo-2-(methylthio)pyrimidine-6-carboxamido)pyridin-3-yl diethylcarbamodithioate

HRID 507543

反応式

HRID 507543 の反応式
[Br:1][C:2]1[C:3]([C:10]([OH:12])=O)=[N:4][C:5]([S:8][CH3:9])=[N:6][CH:7]=1.C(Cl)(=O)C(Cl)=O.C(N(CC)CC)C.[CH2:26]([N:28]([CH2:39][CH3:40])[C:29]([S:31][C:32]1[CH:33]=[N:34][CH:35]=[CH:36][C:37]=1[NH2:38])=[S:30])[CH3:27]>CN(C)C=O.ClCCl>[CH2:39]([N:28]([CH2:26][CH3:27])[C:29]([S:31][C:32]1[CH:33]=[N:34][CH:35]=[CH:36][C:37]=1[NH:38][C:10]([C:3]1[N:4]=[C:5]([S:8][CH3:9])[N:6]=[CH:7][C:2]=1[Br:1])=[O:12])=[S:30])[CH3:40]

参加物

7

反応物 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 2917865-Bromo-2-(methylthio)pyrimidine-4-carboxylic AcidHCID 146662264-Aminopyridin-3-yl diethylcarbamodithioate

生成物 1

HCID 602043714-(5-Bromo-2-(methylthio)pyrimidine-6-carboxamido)pyridin-3-yl diethylcarbamodithioate収率 51%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒2 回

実験手順

A catalytic amount of N,N-dimethylformamide (2 drops) was added to a stirred suspension of 5-bromo-2-(methylthio)pyrimidine4-carboxylic acid (2.07 g, 8.33 mmol) and a 2 M solution of oxalyl chloride (21 mL, 0.042 mol) in dichloromethane under nitrogen at r.t. Vigorous effervescence was observed. After 30 min everything had dissolved and the solvent was then evaporated in vacuo. The residue was dissolved in dichloromethane (20 mL) and placed under nitrogen. Triethylamine (2.32 mL, 16.66 mmol) was added to this stirred solution at r.t. followed by 4-aminopyridin-3-yl diethylcarbamodithioate (2.01 g, 8.33 mmol). Everything quickly dissolved with a noticeable exotherm. After 3 h at r.t. tlc showed a new major product. The reaction was diluted with dichloromethane (20 mL) and washed with a saturated aqueous solution of sodium hydrogen carbonate (40 mL). The organic layer was separated, dried over sodium sulfate, filtered and the solvent evaporated in vacuo. The residue was purified by flash chromatography (ethyl acetate/hexane 15:85 to 60:40) to yield 4-(5-bromo-2-(methylthio)pyrimidine-6-carboxamido)pyridin-3-yl diethylcarbamodithioate (1.99 g, 51%) as a pale yellow amorphous solid. 1H NMR: δ (CDCl3, 400 MHz) 1.30 (t, J=7 Hz, 3H), 1.51 (t, J=7 Hz, 3H), 2.60 (s, 3H), 3.93-4.08 (m, 4H), 8.57-8.62 (m, 2H), 8.69 (d, J=6 Hz, 1H), 8.85 (s, 1H), 10.67 (s, 1H).

後処理

  1. customat r.t
  2. dissolutionAfter 30 min everything had dissolved
  3. customthe solvent was then evaporated in vacuo
  4. dissolutionThe residue was dissolved in dichloromethane (20 mL)
  5. dissolutionEverything quickly dissolved with a noticeable exotherm
  6. washwashed with a saturated aqueous solution of sodium hydrogen carbonate (40 mL)
  7. customThe organic layer was separated
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customthe solvent evaporated in vacuo
  11. customThe residue was purified by flash chromatography (ethyl acetate/hexane 15:85 to 60:40)

出典と根拠

ORDレコード
ord-2203b4f8b11643938e98a88d7fc7aca9
出典データセット
uspto-grants-2010_08
特許番号
US07786132B2

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