Potassium Carbonate → 6-Chloro-1-cyclopropylmethyluracil

HRID 2222228ノート

反応式

HRID 2222228 の反応式
[Cl:1][C:2]1[NH:7][C:6](=[O:8])[NH:5][C:4](=[O:9])[CH:3]=1.C([O-])([O-])=O.[K+].[K+].[CH:16]1([CH2:19]Br)[CH2:18][CH2:17]1.[OH-].[Na+]>CS(C)=O>[Cl:1][C:2]1[N:7]([CH2:19][CH:16]2[CH2:18][CH2:17]2)[C:6](=[O:8])[NH:5][C:4](=[O:9])[CH:3]=1

参加物

6

反応物 4

HCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 732726-ChlorouracilHCID 81503Bromomethylcyclopropane

生成物 1

HCID 179901746-Chloro-1-cyclopropylmethyluracil

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
85 °C

実験手順

6-Chlorouracil I (49.64 g, 0.34 mol; Lancaster) was dissolved in anhydrous DMSO (375 mL) and treated with solid K2CO3 (23.46 g, 0.17 mol) under nitrogen. The resulting white suspension was heated to ca. 80-90° C. and kept at this temperature for 2¼ h. Foaming was observed as the temperature increased, then the reaction mixture became mostly clear. Cyclopropylmethyl bromide (65 g, 0.48 mol) was added neat via syringe, resulting in a white fluffy precipitate. This was followed by a catalytic amount of KI (2.88 g, 0.017 mol). The reaction mixture was heated for 19 hr, becoming mostly homogenous, then turbid with white granular precipitate, and eventually orange as the reaction progressed, remaining heterogeneous. 375 mL 1 N NaOH (aq) was added to the hot reaction mixture, causing it to darken and clear. The heat was removed and the reaction mixture allowed to cool to room temperature while stirring. It was washed with 4×125 mL toluene and the organic washings discarded. The aqueous phase was brought to pH 2-3 by the addition of ca. 100 mL conc. HCl (aq.). 50 mL water was added, and precipitation began after about one hour at room temperature; cooling in ice completed the crystallization. The yellow-green solid was collected by filtration and washed with very cold ether to remove most of the color, then dried under vacuum. Yield: 29.37 g (43%) of a light yellow solid.

後処理

  1. waitkept at this temperature for 2¼ h
  2. temperatureincreased
  3. customresulting in a white fluffy precipitate
  4. temperatureThe reaction mixture was heated for 19 hr
  5. customThe heat was removed
  6. temperatureto cool to room temperature
  7. washIt was washed with 4×125 mL toluene
  8. additionThe aqueous phase was brought to pH 2-3 by the addition of ca. 100 mL conc. HCl (aq.)
  9. addition50 mL water was added
  10. customprecipitation
  11. temperaturecooling in ice
  12. customthe crystallization
  13. filtrationThe yellow-green solid was collected by filtration
  14. washwashed with very cold ether
  15. customto remove most of the color
  16. customdried under vacuum

出典と根拠

ORDレコード
ord-decc79206c0a4357bb7764cc3f710b35
出典データセット
uspto-grants-2008_05
特許番号
US07371757B2

反応ノート

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