Perchloric Acid → (S)-methyl 2-(2-(3-bromophenyl)-7-iodo-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-(tert-butoxy)acetate

HRID 1400693ノート

反応式

HRID 1400693 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([C:8]2[CH:24]=[C:11]3[N:12]=[C:13]([CH3:23])[C:14]([C@H:17]([OH:22])[C:18]([O:20][CH3:21])=[O:19])=[C:15]([I:16])[N:10]3[N:9]=2)[CH:5]=[CH:6][CH:7]=1.Cl(O)(=O)(=O)=O>C(Cl)Cl.C(OC(C)(C)C)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]([C:8]2[CH:24]=[C:11]3[N:12]=[C:13]([CH3:23])[C:14]([C@H:17]([O:22][C:4]([CH3:8])([CH3:5])[CH3:3])[C:18]([O:20][CH3:21])=[O:19])=[C:15]([I:16])[N:10]3[N:9]=2)[CH:5]=[CH:6][CH:7]=1

参加物

5

反応物 2

HCID 24247Perchloric AcidHCID 86710745(S)-methyl 2-(2-(3-bromophenyl)-7-iodo-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-hydroxyacetate

生成物 1

HCID 86710746(S)-methyl 2-(2-(3-bromophenyl)-7-iodo-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-(tert-butoxy)acetate収率 143.9%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 10908tert-Butyl acetate溶媒

実験手順

To a stirred solution of (S)-methyl 2-(2-(3-bromophenyl)-7-iodo-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-hydroxyacetate (1 g, 1.992 mmol) in CH2Cl2 (30 mL) and t-butyl acetate (21.00 mL) at rt was added 70% perchloric acid (0.513 mL, 5.97 mmol). After 3 h, the reaction mixture was diluted with CH2Cl2 (100 mL), carefully quenched with sat. NaHCO3 (50 mL), organic layer separated and washed with brine (100 mL), dried (Na2SO4), filtered and concentrated to give yellow liquid. This was purified by flash column chromatograpgy on silica gel column using (10-50% EtOAc/Hex as eluant) to afford (S)-methyl 2-(2-(3-bromophenyl)-7-iodo-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-(tert-butoxy)acetate (800 mg, 1.433 mmol, 72.0% yield) as yellow solid. 1H NMR (500 MHz, CDCl3) δ: 8.20 (s, 1H), 7.95 (d, J=7.7 Hz, 1H), 7.56 (d, J=7.9 Hz, 1H), 7.37 (t, J=7.9 Hz, 1H), 7.08 (s, 1H), 5.59 (s, 1H), 3.76 (s, 3H), 2.70 (s, 3H), 1.32 (s, 9H). LCMS (M+H)=560.15.

後処理

  1. customcarefully quenched with sat. NaHCO3 (50 mL), organic layer
  2. customseparated
  3. washwashed with brine (100 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give yellow liquid
  8. customThis was purified by flash column chromatograpgy on silica gel column

出典と根拠

ORDレコード
ord-e549e393babf45018191c6c6e1a6d4be
出典データセット
uspto-grants-2014_12
特許番号
US08906929B2

反応ノート

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