Phosgene → 7-isocyanato-4-methyl-2H-chromen-2-one

HRID 2061377ノート

反応式

HRID 2061377 の反応式
[C:1](Cl)(Cl)=[O:2].[NH2:5][C:6]1[CH:15]=[C:14]2[C:9]([C:10]([CH3:17])=[CH:11][C:12](=[O:16])[O:13]2)=[CH:8][CH:7]=1>C1(C)C=CC=CC=1.O1CCOCC1>[N:5]([C:6]1[CH:15]=[C:14]2[C:9]([C:10]([CH3:17])=[CH:11][C:12](=[O:16])[O:13]2)=[CH:8][CH:7]=1)=[C:1]=[O:2]

参加物

5

反応物 2

HCID 6371PhosgeneHCID 922497-Amino-4-methylcoumarin

生成物 1

HCID 583781007-isocyanato-4-methyl-2H-chromen-2-one収率 25%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

A 200-mL three-neck flask fitted with a dry ice condenser and magnetic stirrer was charged with a solution of 20% phosgene in toluene solution (2.0 mL) and dioxane (80 mL). To this mixture was added 7-amino-4-methyl-2H-chromen-2-one (2.00 g, 11.4 mmol). The mixture was stirred at 100° C. for 12 h. The initial yellow colour disappeared and a white solid precipitated. An additional 20% phosgene in toluene solution (7.0 mL) was added and the mixture heated for an additional 5 h, at which time the solution cleared. Excess phosgene and traces of HCl was removed by bubbling nitrogen gas through the solution. The cloudy solution was filtered to remove unreacted 7-amino-4-methyl-2H-chromen-2-one and concentrated to give 76 (0.5 g, 25%) as a white solid. H1 NMR (500 MHz, CDCl3): δ=7.50 (1H, d, J=7.40 Hz, ArH), 7.46 (2H, s, ArH), 6.20 (1H, s, ArH), 2.35 (3H, s, CH3): ir (CH2CL2) 2314 (N═C═O), 1726 and 1615 cm−1.

後処理

  1. customA 200-mL three-neck flask fitted with a dry ice condenser and magnetic stirrer
  2. customa white solid precipitated
  3. additionAn additional 20% phosgene in toluene solution (7.0 mL) was added
  4. temperaturethe mixture heated for an additional 5 h, at which time the solution
  5. customExcess phosgene and traces of HCl was removed
  6. customby bubbling nitrogen gas through the solution
  7. filtrationThe cloudy solution was filtered
  8. customto remove unreacted 7-amino-4-methyl-2H-chromen-2-one
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-4cfcdfbea8074b608028271eb26a4f07
出典データセット
uspto-grants-2012_10
特許番号
US08283340B2

反応ノート

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