Benzonitrile, m-chloro- → Methyl 2-(2-chloro-4-cyanophenyl)acetate

HRID 76865

反応式

HRID 76865 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[C:5]#[N:6].[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[C:20]([C:22]([O:24][CH3:25])=[O:23])#N>C1COCC1>[CH3:25][O:24][C:22](=[O:23])[CH2:20][C:9]1[CH:8]=[CH:7][C:4]([C:5]#[N:6])=[CH:3][C:2]=1[Cl:1]

参加物

5

反応物 3

HCID 13015Benzonitrile, m-chloro-HCID 28660Carbonocyanidic acid, methyl esterHCID 2733832Lithium Hexamethyldisilazide

生成物 1

HCID 86611068Methyl 2-(2-chloro-4-cyanophenyl)acetate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

4-{5-[2-tert-Butyldimethylsilanyloxy)ethyl]imidazol-1-ylmethyl}-3-chlorobenzonitrile (1.7 g, 4.52 mmol) is dissolved in anhydrous THF (30 mL) and stirred at −78° C. before a THF solution of LHMDS (8.1 mL, 1.0 M) is added. After 15 min, methyl cyanoformate (0.38 mL, 4.74 mmol) is added and the solution is left at −78° C. for 2 h. The excess LHMDS is quenched with aqueous saturated NH4Cl and the mixture is allowed to warm to room temperature. The mixture is then diluted with EtOAc and washed with aqueous saturated NH4Cl (2×). Organic is dried (Na2SO4) and evaporated. The crude residue is purified via flash column chromatography (EtOAc/hexanes 1:1→EtOAc) to give {5-[2-tert-butyldimethylsilanyloxy)ethyl]-imidazol-1-yl}-(2-chloro-4-cyanophenyl)acetic acid methyl ester as an oil. MS (ESI) m/z 434.3, 436.3 (M+H).

後処理

  1. additionis added
  2. waitthe solution is left at −78° C. for 2 h
  3. customThe excess LHMDS is quenched with aqueous saturated NH4Cl
  4. additionThe mixture is then diluted with EtOAc
  5. washwashed with aqueous saturated NH4Cl (2×)
  6. dry with materialOrganic is dried (Na2SO4)
  7. customevaporated
  8. customThe crude residue is purified via flash column chromatography (EtOAc/hexanes 1:1→EtOAc)

出典と根拠

ORDレコード
ord-dfb441574fa942208fb18e6416ac21d7
出典データセット
uspto-grants-2014_09
特許番号
US08835646B2

関連ノート

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