Hydrochloric Acid → Methyl 2-Benzoylnicotinate

HRID 128934

反応式

HRID 128934 の反応式
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]2[C:7]([O:9][C:10](=[O:11])[C:2]=12)=[O:8].[C:12]1([Mg]Br)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.Cl.OS(O)(=O)=O.[CH2:26]1COCC1>CO.ClCCl>[C:10]([C:2]1[N:1]=[CH:6][CH:5]=[CH:4][C:3]=1[C:7]([O:9][CH3:26])=[O:8])(=[O:11])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 8028TetrahydrofuranHCID 69688Furo[3,4-b]pyridine-5,7-dioneHCID 178418255HCID 178418255、化合物

生成物 1

HCID 19700681Methyl 2-Benzoylnicotinate収率 26%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
21 °C

実験手順

To a suspension of 29.84 grams 2,3-pyridinedicarboxylic anhydride in 300 ml THF under an atmosphere of dry nitrogen was added dropwise 200 ml of a 1.0M solution of phenyl magnesium bromide at -78° C. After two hours the reaction mixture was warmed to 21° C. and stirred overnight. The mixture was then refluxed for 24 hours, cooled, treated with 220 ml 1N HCl, stirred one hour, and transferred to separatory funnel. The THF layer was dried over magnesium sulfate, filtered and concentrated under vacuum to give 44.26 grams crude material which was then dissolved in 400 ml anhydrous methanol. To this solution was carefully added 10 ml conc. H2SO4. The solution was then refluxed overnight under an atmosphere of nitrogen. The mixture was cooled and concentrated under vacuum, neutralized with saturated sodium carbonate solution, and extracted with dichloromethane. The mixture was then dried over magnesium sulfate, filtered and concentrated under vacuum to give 42.71 grams crude material. The crude material was dissolved with a minimum amount of dichloromethane and treated by silica gel [column chromatography, eluted with ethyl acetate/hexane (1:3)] to give 12.35 grams (26% yield) of the desired methyl 2-benzoylnicotinate as a white powder. Characteristic analytical data are as follows: mp 74° C.; TLC in 1:3 EtOAc/Hex; 1H NMR (CDCl3, 300 MHz) δ3.77 (s, 3H), 7.45-7.85 (m, 6H), 8.37 (dd, 1H, J=8.0, 1.6 Hz), 8.82 (dd, 1H, J=4.8, 1.5 Hz); mass spectrum (EI), m/e 421.

後処理

  1. temperatureThe mixture was then refluxed for 24 hours
  2. temperaturecooled
  3. stirringstirred one hour
  4. customtransferred to separatory funnel
  5. dry with materialThe THF layer was dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customto give 44.26 grams crude material which
  9. temperatureThe solution was then refluxed overnight under an atmosphere of nitrogen
  10. temperatureThe mixture was cooled
  11. concentrationconcentrated under vacuum
  12. extractionextracted with dichloromethane
  13. dry with materialThe mixture was then dried over magnesium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated under vacuum
  16. customto give 42.71 grams crude material
  17. additiontreated by silica gel [column chromatography, eluted with ethyl acetate/hexane (1:3)]

出典と根拠

ORDレコード
ord-11d3045bbf9d421a9c57bf68abb8488b
出典データセット
uspto-grants-1995_11
特許番号
US05466697

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