p-Toluenesulfonic acid monohydrate → HCID 67212603, 화합물

HRID 1671339노트

반응식

HRID 1671339 반응식
[CH2:1]([O:3][C:4]([C:6]1[C:7]([O:12][CH:13]([CH3:24])[C:14]([C:16]2[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][C:17]=2[CH3:23])=O)=[N:8][NH:9][C:10]=1[CH3:11])=[O:5])[CH3:2].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1.CC(O)=O>[CH2:1]([O:3][C:4]([C:6]1[C:10]([CH3:11])=[N:9][N:8]2[C:14]([C:16]3[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][C:17]=3[CH3:23])=[C:13]([CH3:24])[O:12][C:7]=12)=[O:5])[CH3:2]

참가 물질

5

반응물 2

HCID 521998p-Toluenesulfonic acid monohydrateHCID 178470036HCID 178470036, 화합물

생성물 1

HCID 67212603HCID 67212603, 화합물수율 88%

시약·촉매·용매 2

HCID 176Acetic Acid용매HCID 1140Toluene용매

실험 절차

A mixture of 3-[2-(2,4-dimethyl-phenyl)-1-methyl-2-oxo-ethoxy]-5-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (273 mg, 0.83 mmol), para-toluenesulfonic acid mono-hydrate (160 mg, 0.83 mmol) in toluene (15 ml) and AcOH (5 ml) is refluxed for 3 days. The reaction mixture is concentrated in vacuo and the residue is dissolved in EtOAc (40 ml). The organic solution is washed successively with Na2CO3 2M in water (2×20 ml) and brine (20 ml), dried over Na2SO4, filtered and concentrated to dryness. The resulting crude residue is purified by Combi-Flash Companion™ (Isco Inc.) column chromatography (SiO2; gradient elution, iso-hexane/TBME 98:2→7:3) to yield the title compound (227 mg, 0.73 mmol, 88%) as a colorless oil. TLC: RF=0.81 (iso-hexane/TBME 1:1); HPLC: AtRet=2.85; MS: m/z 313.2 [M+H]+; 1H NMR (400 MHz, DMSO-d6) δ 1.30 (t, J 7.1, 3H), 2.20 (s, 3H), 2.34 (s, 3H), 2.36 (s, 3H), 2.41 (s, 3H), 4.26 (q, J 7.1, 2H), 7.17 (m, 1H), 7.24 (br. s., 1H), 7.31 (m, 1H).

후처리

  1. temperatureis refluxed for 3 days
  2. concentrationThe reaction mixture is concentrated in vacuo
  3. dissolutionthe residue is dissolved in EtOAc (40 ml)
  4. washThe organic solution is washed successively with Na2CO3 2M in water (2×20 ml) and brine (20 ml)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness
  8. customThe resulting crude residue is purified by Combi-Flash Companion™ (Isco Inc.) column chromatography (SiO2; gradient elution, iso-hexane/TBME 98:2→7:3)

출처 및 근거

ORD 기록
ord-8e681e4d263a4477b842c2f124bc5b99
출처 데이터셋
uspto-grants-2011_08
특허 번호
US07994203B2

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