Diazomethane → Methyl 2-((tert-butoxycarbonyl)amino)-5-(trifluoromethyl)benzoate

HRID 1006547ノート

反応式

HRID 1006547 の反応式
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C([Li])(C)(C)C.[N+](=C)=[N-]>C1COCC1.CCOCC>[C:1]([O:5][C:6]([NH:8][C:9]1[CH:10]=[CH:11][C:12]([C:15]([F:16])([F:17])[F:18])=[CH:13][C:14]=1[C:6]([O:5][CH3:1])=[O:7])=[O:7])([CH3:4])([CH3:2])[CH3:3]

参加物

6

反応物 3

HCID 9550DiazomethaneHCID 112307451,1-Dimethylethyl N-[4-(trifluoromethyl)phenyl]carbamateHCID 178418306HCID 178418306、化合物

生成物 1

HCID 22672049Methyl 2-((tert-butoxycarbonyl)amino)-5-(trifluoromethyl)benzoate収率 159.4%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒2 回HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-30 °C

実験手順

4-t-butoxycarbonylaminobenzotrifluoride (3.90 g) was dissolved in THF. At −50° C., t-butyl lithium (30 ml) was added dropwise thereto. The mixture was stirred for 3 hours with keeping at −50° C. Carbon dioxide gas was bubbled into this mixture under stirring (the temperature increased to about −30° C.). The solvent was distilled out. The back-extractration of the residue was 2N NaOH-ether mixture solution was carried out. The aqueous layer was acidified by adding 2N HCl, extracted with ether, washed and dried over. In addition, the layer containing ether was washed, dried over, filtered and concentrated after combining the said layer containing ether to give the crude compound. Such crude compound was dissolved in ether. A solution of diazomethane in ether was added thereto until the reaction solution became yellow. The reaction solution was concentrated and purified on silica gel column chromatography (hexane:AcOEt=20:1→10:1) to give the title compound (3.80 g) having the following physical data.

後処理

  1. customwith keeping at −50° C
  2. customCarbon dioxide gas was bubbled into this mixture
  3. stirringunder stirring (the temperature
  4. distillationThe solvent was distilled out
  5. additionby adding 2N HCl
  6. extractionextracted with ether
  7. washwashed
  8. customdried over
  9. additionIn addition, the layer containing ether
  10. washwas washed
  11. customdried over,
  12. filtrationfiltered
  13. concentrationconcentrated
  14. additioncontaining ether
  15. customto give the crude compound
  16. concentrationThe reaction solution was concentrated
  17. custompurified on silica gel column chromatography (hexane:AcOEt=20:1→10:1)

出典と根拠

ORDレコード
ord-d0eda1b0d9724c5fbe7b0b02cfc0ba69
出典データセット
uspto-grants-2004_09
特許番号
US06790866B2

反応ノート

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