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Lithium Chloride → Pyriofenone

HRID 242438
ノート
印刷プレビュー

反応式

HRID 242438 の反応式
C([Mg]Cl)(C)C.Br[C:7]1[C:8]([O:15][CH3:16])=[N:9][CH:10]=[C:11]([Cl:14])[C:12]=1[CH3:13].ClC1C(C)=C([Mg]Cl)C(OC)=NC=1.[Cu]C#N.[Cl-].[Li+].ClC1C(C)=C([Cu])C(OC)=NC=1.[CH3:45][O:46][C:47]1[C:55]([O:56][CH3:57])=[C:54]([O:58][CH3:59])[CH:53]=[C:52]([CH3:60])[C:48]=1[C:49](O)=[O:50].N1C=CC=CC=1[Cu].O.N>O1CCCC1.S(Cl)(Cl)=O.O>[CH3:45][O:46][C:47]1[C:55]([O:56][CH3:57])=[C:54]([O:58][CH3:59])[CH:53]=[C:52]([CH3:60])[C:48]=1[C:49]([C:7]1[C:8]([O:15][CH3:16])=[N:9][CH:10]=[C:11]([Cl:14])[C:12]=1[CH3:13])=[O:50]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

13

反応物 9

HCID 433294Lithium ChlorideHCID 12896473Azane;hydrateHCID 135314152,3,4-Trimethoxy-6-methylbenzoic acidHCID 231336453-Bromo-5-chloro-2-methoxy-4-methylpyridineHCID 178418546HCID 178418546、化合物HCID 178418918HCID 178418918、化合物HCID 178494192HCID 178494192、化合物
HCID 178494194
HCID 178494194、化合物
HCID 178505376CID 178270706

生成物 1

HCID 23082663Pyriofenone収率 107.7%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 24386Thionyl Chloride溶媒

反応条件

温度
-78 °C

実験手順

(b-1) 6.8 ml (13.6 mmol) of isopropylmagnesium chloride (2M tetrahydrofuran solution) was cooled to 0° C., and a solution having 1.6 g (6.6 mmol) of 3-bromo-5-chloro-2-methoxy-4-methylpyridine dissolved in 5 ml of tetrahydrofuran was dropwise added, followed by stirring at the same temperature for 3 hours to prepare 5-chloro-2-methoxy-4-methyl-3-pyridylmagnesium chloride. The reaction solution was cooled to −78° C., and a solution having 1.2 g (13.3 mmol) of copper(I) cyanide and 1.15 g (27.1 mmol) of lithium chloride dissolved in 15 ml of tetrahydrofuran was dropwise added to prepare a 5-chloro-2-methoxy-4-methyl-3-pyridylcopper reagent. Separately, 3.2 g (14.3 mmol) of 2,3,4-trimethoxy-6-methylbenzoic acid prepared in Step (a) was subjected to reflux with heating in 7 ml of thionyl chloride for 3 hours, and the surplus thionyl chloride was distilled off under reduced pressure to prepare 2,3,4-trimethoxy-6-methylbenzoyl chloride, which was dissolved in 7 ml of tetrahydrofuran. The solution thus prepared was dropwise added at −78° C. to the above prepared pyridylcopper reagent, followed by stirring for 1 hour, and the temperature was increased to room temperature, followed by stirring further for 2 hours. Water and ammonia water were added to the reaction solution to terminate the reaction, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and subjected to filtration, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography to obtain 2.6 g (yield: 57%) of 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-chloro-2-methoxy-4-methylpyridine (melting point 85 to 88° C.), and the compound was identified by 1HNMR.

後処理

  1. additionwas dropwise added
  2. additionwas dropwise added
  3. temperatureto reflux
  4. distillationthe surplus thionyl chloride was distilled off under reduced pressure
  5. customto prepare 2,3,4-trimethoxy-6-methylbenzoyl chloride, which
  6. customThe solution thus prepared
  7. additionwas dropwise added at −78° C. to the
  8. stirringby stirring for 1 hour
  9. temperaturethe temperature was increased to room temperature
  10. stirringby stirring further for 2 hours
  11. customto terminate
  12. customthe reaction
  13. extractionfollowed by extraction with ethyl acetate
  14. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  15. filtrationsubjected to filtration
  16. distillationthe solvent was distilled off under reduced pressure
  17. customThe crude product was purified by silica gel column chromatography

出典と根拠

ORDレコード
ord-21e4f3d3171747dd9ee2f5ed30f57b1b
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08653113B2

反応ノート

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