Dimethylformamide → Methyl 2-vinylnicotinate

HRID 274854

反応式

HRID 274854 の反応式
Cl[C:2]1[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1.[CH:12]([Sn](CCCC)(CCCC)CCCC)=[CH2:13].C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.CN(C)C=O>[Pd].C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[CH:12]([C:2]1[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1)=[CH2:13]

参加物

8

反応物 4

HCID 6228DimethylformamideHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 81998Tributylvinyltin2 回HCID 819931Methyl 2-chloronicotinate

生成物 1

HCID 21862216Methyl 2-vinylnicotinate

試薬・触媒・溶媒 3

HCID 23938Palladium触媒HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
55 °C

実験手順

2-Ethenyl-3-pyridinecarboxylic acid, methyl ester (12) is prepared as follows: a mixture of 19.7 g (115 mmol) of 2-chloro-3-pyridinecarboxylic acid, methyl ester (11), 38.3 g (120.8 mmol) of vinyltributyltin, 1.48 g (2.1 mmol) of bis(triphenylphosphine)palladium (II) chloride 100 mg of 2,6-ditertbutyl-4-methylphenol, and 250 mL of N,N-dimethylformamide is stirred at 55° C. for 7 hours, then treated with 1.63 g 15.1 mmol) of additional vinyltributyltin and 1 g of palladium catalyst. The mixture is heated further at 40° C. for 61 hours, then concentrated at 60° C./5 mm to leave a greenish oil that is dissolved in ethyl acetate and filtered through a pad of silica gel (230-400 mesh). The filtrate is diluted with additional ethyl acetate and the organic phase is washed with water, dried, and concentrated to an oil. The oil is distilled, with material collected in the 80°-95° C./0.14 mm ranger to leave 24.5 g of an oil that is ca. 75% product by GC. The oil is dissolved in dichloromethane:hexanes (1:1) and loaded onto an 8 x 15 cm of silica gel column (230-400 mesh). The column is eluted with the same solvent as above with 500 mL fractions collected. Product fractions are combined and carefully distilled at 65°-67° C./0.15 mm to leave 13.6 g of clear oil, >95% pure by GC, that is sufficiently pure to use directly in the next step.

後処理

  1. temperatureThe mixture is heated further at 40° C. for 61 hours
  2. concentrationconcentrated at 60° C./5 mm
  3. customto leave a greenish oil that
  4. filtrationfiltered through a pad of silica gel (230-400 mesh)
  5. additionThe filtrate is diluted with additional ethyl acetate
  6. washthe organic phase is washed with water
  7. customdried
  8. concentrationconcentrated to an oil
  9. distillationThe oil is distilled, with material
  10. customcollected in the 80°-95° C./0.14 mm ranger

出典と根拠

ORDレコード
ord-b7b5d8a724604f80800b2e11dc4c62c3
出典データセット
uspto-grants-1995_02
特許番号
US05391554

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