Nitric Acid → Methyl 4-cyano-2-methyl-5-nitrobenzoate

HRID 906151ノート

反応式

HRID 906151 の反応式
[C:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:13])[CH:4]=1)#[N:2].[N+:14]([O-])([OH:16])=[O:15]>S(=O)(=O)(O)O>[C:1]([C:3]1[C:12]([N+:14]([O-:16])=[O:15])=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:13])[CH:4]=1)#[N:2]

参加物

4

反応物 2

HCID 944Nitric AcidHCID 18766060Methyl 4-cyano-2-methylbenzoate

生成物 1

HCID 67403131Methyl 4-cyano-2-methyl-5-nitrobenzoate収率 65%

試薬・触媒・溶媒 1

HCID 1118Sulfuric Acid溶媒

反応条件

温度
0 °C

実験手順

A solution of methyl 4-cyano-2-methylbenzoate (18.1 g, 0.103 mol) in concentrated sulfuric acid (130 mL) was cooled to −10° C. While maintaining this internal temperature, fuming nitric acid (15.6 mL) was slowly added over a period of 30 min. The reaction mixture was stirred an additional 2.5 h at 0° C., at which time it was poured over 1.0 L of ice and then partitioned with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate, brine, dried over anhydrous magnesium sulfate, and then concentrated in vacuo. The residue was triturated with 10% ethyl acetate/hexanes to afford methyl 4-cyano-2-methyl-5-nitrobenzoate (14.8 g, 65%) as a white powder. The title product was isolated as the major isomer in a 9:1 regioisomeric mixture. 1H NMR (400 MHz, CDCl3), Major: 8.85 (s, 1H), 7.81 (s, 1H), 4.00 (s, 3H), 2.77 (s, 3H); Minor: 8.07 (d, 1H), 7.72 (d, 1H), 3.98 (s, 3H), 2.57 (s, 3H). MS (EI) for C10H8N2O4: 238 (M+H2O).

後処理

  1. additionwas slowly added over a period of 30 min
  2. custompartitioned with ethyl acetate
  3. washThe organic layer was washed with saturated sodium bicarbonate, brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was triturated with 10% ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-aed4a1c0ca014ff9b47107ed3405de54
出典データセット
uspto-grants-2011_09
特許番号
US08012956B2

反応ノート

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