Triethylamine → 2-Ethoxy-5-(4-ethyl-1-piperazinylsulfonyl)benzonitrile

HRID 433649

反応式

HRID 433649 の反応式
[CH2:1]([O:3][C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[C:6]#[N:7])[CH3:2].Cl[S:13]([OH:16])(=O)=[O:14].S(Cl)(Cl)=O.C(N(CC)CC)C.[CH2:28]([N:30]1[CH2:35][CH2:34][NH:33][CH2:32][CH2:31]1)[CH3:29]>>[CH2:1]([O:3][C:4]1[CH:11]=[CH:10][C:9]([S:13]([N:33]2[CH2:34][CH2:35][N:30]([CH2:28][CH3:29])[CH2:31][CH2:32]2)(=[O:16])=[O:14])=[CH:8][C:5]=1[C:6]#[N:7])[CH3:2]

参加物

6

反応物 5

HCID 8471TriethylamineHCID 24386Thionyl ChlorideHCID 24638Chlorosulfonic acidHCID 791961-EthylpiperazineHCID 5769222-Ethoxybenzonitrile

生成物 1

HCID 99670112-Ethoxy-5-(4-ethyl-1-piperazinylsulfonyl)benzonitrile収率 17.8%

実験手順

Commercially available 2-ethoxybenzonitrile (25 g, 0.17 Mol) was added dropwise to an ice cooled mixture of chlorosulfonic acid (50.8 mL, 0.765 Mol) and thionyl chloride (12.4 mL, 0.17 Mol) so as to keep the temperature below 10° C. The reaction was then stirred at ambient temperature for 18 h before being poured onto ice/water. This mixture was stirred 1 hr before the precipitated material was filtered off. The resultant solid was dissolved in acetone (300 mL) and triethylamine (25 mL, 0.179 Mol) was added followed by a slow addition of N-ethylpiperazine (25 mL, 0.198 Mol). After being left at ambient temperature for 65 h the mixture was evaporated and the residue stirred with water (1 L) for 2 h. The solids were filtered off, washed with water and dried before being chromatographed over silica gel using ethyl acetate methanol mixtures. Combination and evaporation of like fractions yielded 9.8 g, 17.8% of the title compound. Melting point=86-88° C. M/Z=324 (M+H). 300 MHz Proton NMR (CDCl3); 1.06 (t, 3H), 1.55 (t, 3H), 2.43 (q, 2H), 2.54 (m, 4H), 3.06 (m, 4H), 4.25 (q, 2H), 7.08 (d 1H), 7.90 (dd, 1H), 7.97 (d,1H).

後処理

  1. temperaturecooled
  2. customthe temperature below 10° C
  3. additionbefore being poured onto ice/water
  4. stirringThis mixture was stirred 1 hr before the precipitated material
  5. filtrationwas filtered off
  6. dissolutionThe resultant solid was dissolved in acetone (300 mL)
  7. waitAfter being left at ambient temperature for 65 h the mixture
  8. customwas evaporated
  9. stirringthe residue stirred with water (1 L) for 2 h
  10. filtrationThe solids were filtered off
  11. washwashed with water
  12. customdried
  13. custombefore being chromatographed over silica gel
  14. customCombination and evaporation of like fractions

出典と根拠

ORDレコード
ord-84c58b1a9951452fad762f2f4a339122
出典データセット
uspto-grants-2003_12
特許番号
US06667398B2

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