Methyl 3-chloro-2-nitrobenzoate → Benzoic acid, 2-amino-3-chloro-, methyl ester

HRID 132382ノート

反応式

HRID 132382 の反応式
[Cl:1][C:2]1[C:3]([N+:12]([O-])=O)=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]>CCO.CC(O)=O.[Fe]>[NH2:12][C:3]1[C:2]([Cl:1])=[CH:11][CH:10]=[CH:9][C:4]=1[C:5]([O:7][CH3:8])=[O:6]

参加物

4

反応物 1

HCID 12187125Methyl 3-chloro-2-nitrobenzoate

生成物 1

HCID 11030511Benzoic acid, 2-amino-3-chloro-, methyl ester収率 79%

試薬・触媒・溶媒 2

HCID 23925Iron触媒HCID 18476134Acetic acid ethanol溶媒

実験手順

Iron powder (1.94 g, 34.8 mmol) was added to the solution of methyl 3-chloro-2-nitrobenzoate (2.5 g, 11.6 mmol) in EtOH/HOAc (100 mL/100 mL) at room temperature, and then the suspension was refluxed under N2 for 2 hrs. After cooling down to room temperature, partial of the solvents was removed on rotary vacuum, the resulting residue was partitioned between H2O/EtOAc (200 mL/300 mL). The separated organic phase was washed with aqueous NaOH (1N, 50 mL), brine (50 mL), dried over MgSO4, and concentrated on rotary vacuum to afford the expected product as a tan oil (1.7 g, 79% yield) which became wax type solid standing on bench. The crude product was pure enough to be used in next step without further purification; 1H NMR (400 MHz, CDCl3) δ ppm 3.86 (s, 3 H), 6.25 (s, 2 H), 6.57 (t, J=7.93 Hz, 1 H), 7.39 (dd, J=7.81, 1.51 Hz, 1 H), 7.79 (dd, J=8.06, 1.51 Hz, 1 H); Mass spec. 185.95 (MH+), Calc. for C8H8ClNO2 185.02.

後処理

  1. temperaturethe suspension was refluxed under N2 for 2 hrs
  2. customwas removed on rotary vacuum
  3. customthe resulting residue was partitioned between H2O/EtOAc (200 mL/300 mL)
  4. washThe separated organic phase was washed with aqueous NaOH (1N, 50 mL), brine (50 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated on rotary vacuum

出典と根拠

ORDレコード
ord-d99bd0e5c2124c20826e66dbed6c8e71
出典データセット
uspto-grants-2008_06
特許番号
US07384931B2

反応ノート

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