Ethanesulfonamide → N-((5-bromopyridin-3-yl)(cyclopentyl)methyl)ethanesulfonamide

HRID 1897782ノート

反応式

HRID 1897782 の反応式
[Br:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:9]=1)[CH:7]=O.[CH2:10]([S:12]([NH2:15])(=[O:14])=[O:13])[CH3:11].[CH:16]1([Mg]Br)[CH2:20][CH2:19][CH2:18][CH2:17]1>C1(C)C=CC=CC=1.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[Br:1][C:2]1[CH:9]=[C:6]([CH:7]([CH:16]2[CH2:20][CH2:19][CH2:18][CH2:17]2)[NH:15][S:12]([CH2:10][CH3:11])(=[O:14])=[O:13])[CH:5]=[N:4][CH:3]=1

参加物

6

反応物 3

HCID 73702EthanesulfonamideHCID 27847345-Bromo-3-pyridinecarboxaldehydeHCID 178419650HCID 178419650、化合物

生成物 1

HCID 59578440N-((5-bromopyridin-3-yl)(cyclopentyl)methyl)ethanesulfonamide収率 27.6%

試薬・触媒・溶媒 2

HCID 11026Titanium isopropoxide触媒HCID 1140Toluene溶媒

反応条件

温度
-40 °C

実験手順

A mixture of 5-bromonicotinaldehyde (930 mg, 5 mmol), ethanesulfonamide (546 mg, 5.00 mmol) and titanium(IV) isopropoxide (2930 μl, 10.00 mmol) in toluene (20 mL) was heated to reflux for 4 h. After concentration, the residue was dissolved in THF (25 mL) and cooled to −40° C. A solution of cyclopentylmagnesium bromide (2M in THF, 6.25 mL, 12.5 mmol) was added dropwise and the resulting mixture was slowly warmed up to 0° C. over 4 h. The reaction was quenched with a saturated NH4Cl solution. The mixture was filtered, separated, and extracted with CH2Cl2. The organic phase was dried over Na2SO4, filtered and concentrated, and the residue was purified by flash column (ethyl acetate/heptane, v/v, 10%-30%) to give a yellow oil (480 mg). ESI-MS m/z: 348.9 [M+1]+; 1H NMR (400 MHz, CDCl3): δ 1.13-1.80 (m, 7H), 1.26 (t, J=7.4 Hz, 3H), 1.97-2.05 (m, 1H), 2.20-2.29 (m, 1H), 2.67-2.92 (m, 2H), 4.27 (t, J=8.8 Hz, 1H), 5.59 (brs, 1H), 7.87 (s, 1H), 8.56 (s, 1H), 8.68 (s, 1H).

後処理

  1. temperaturewas heated
  2. temperatureto reflux for 4 h
  3. concentrationAfter concentration
  4. dissolutionthe residue was dissolved in THF (25 mL)
  5. temperaturethe resulting mixture was slowly warmed up to 0° C. over 4 h
  6. customThe reaction was quenched with a saturated NH4Cl solution
  7. filtrationThe mixture was filtered
  8. customseparated
  9. extractionextracted with CH2Cl2
  10. dry with materialThe organic phase was dried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customthe residue was purified by flash column (ethyl acetate/heptane, v/v, 10%-30%)

出典と根拠

ORDレコード
ord-d7e825ed9935430398831b25d3039397
出典データセット
uspto-grants-2013_08
特許番号
US08519142B2

反応ノート

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