4-Chloro-3,5-dinitrobenzonitrile → 3,5-Diamino-4-chlorobenzonitrile

HRID 921862ノート

反応式

HRID 921862 の反応式
[Cl:1][C:2]1[C:9]([N+:10]([O-])=O)=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:13]([O-:15])=[O:14]>[Fe].C(O)(=O)C>[NH2:10][C:9]1[CH:8]=[C:5]([CH:4]=[C:3]([N+:13]([O-:15])=[O:14])[C:2]=1[Cl:1])[C:6]#[N:7].[NH2:13][C:3]1[CH:4]=[C:5]([CH:8]=[C:9]([NH2:10])[C:2]=1[Cl:1])[C:6]#[N:7]

参加物

5

反応物 1

HCID 160084-Chloro-3,5-dinitrobenzonitrile

生成物 2

HCID 124029953,5-Diamino-4-chlorobenzonitrileHCID 717559993-Amino-4-chloro-5-nitrobenzonitrile

試薬・触媒・溶媒 2

HCID 23925Iron触媒HCID 176Acetic Acid溶媒

反応条件

温度
110 °C

実験手順

A 3-neck round bottom flask was equipped with a condenser. The flask was loaded with 4-chloro-3,5-dinitrobenzonitrile (4.5 g, 19.18 mmol) and acetic acid (60 mL). The solution was heated to 110° C. Iron (powder) (2.5 g, 44.8 mmol) was added slowly (in three portions), saw bubbling and also color changed to dark red. The mixture was stirred vigorously for 2 h at 110° C. LC-MS indicated desired monoamine and diamine. Then it was cooled to room temperature and diluted with DCM and saturated aqueous sodium bicarbonate solution was slowly added to neutralize. After separating the layers, the aqueous layer was further extracted with DCM. The combined organic extracts were washed with water, brine, dried over MgSO4, filtered and concentrated. Purification via flash chromatography (0-20% EtOAc in DCM, 120 g) gave 3-amino-4-chloro-5-nitrobenzonitrile (1.8 g) and 3,5-diamino-4-chlorobenzonitrile (1 g) as bright yellow solid and brown solid respectively.

後処理

  1. customA 3-neck round bottom flask was equipped with a condenser
  2. customsaw bubbling
  3. temperatureThen it was cooled to room temperature
  4. additiondiluted with DCM and saturated aqueous sodium bicarbonate solution
  5. additionwas slowly added
  6. customAfter separating the layers
  7. extractionthe aqueous layer was further extracted with DCM
  8. washThe combined organic extracts were washed with water, brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification via flash chromatography (0-20% EtOAc in DCM, 120 g)

出典と根拠

ORDレコード
ord-4b4132db900b45ec935f5b07d43374ec
出典データセット
uspto-grants-2016_03
特許番号
US09273057B2

反応ノート

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