Acrylonitrile → (E)-Methyl 3-(2-cyanovinyl)picolinate

HRID 716007ノート

反応式

HRID 716007 の反応式
Br[C:2]1[C:3]([C:8]([O:10][CH3:11])=[O:9])=[N:4][CH:5]=[CH:6][CH:7]=1.[C:12](#[N:15])[CH:13]=[CH2:14].C1(CNCC2CCCCC2)CCCCC1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[C:12](/[CH:13]=[CH:14]/[C:2]1[C:3]([C:8]([O:10][CH3:11])=[O:9])=[N:4][CH:5]=[CH:6][CH:7]=1)#[N:15]

参加物

8

反応物 4

HCID 7855AcrylonitrileHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 4594378Bis(cyclohexylmethyl)amineHCID 12828946Methyl 3-bromo-2-pyridinecarboxylate

生成物 1

HCID 66818972(E)-Methyl 3-(2-cyanovinyl)picolinate

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

A microwave vial were charged with methyl 3-bromopicolinate (2.84 g, 13.15 mmol), acrylonitrile (0.907 g, 17.09 mmol), N,N-dicyclohexylmethylamine (3.08 g, 15.78 mmol), tri-tert-butylphosphine (0.789 mL, 0.789 mmol, 1 M in toluene), tris(dibenzylideneacetone)dipalladium (0) (0.361 g, 0.394 mmol) and 10 mL of 1,4-dioxane under nitrogen. The reaction mixture was capped and heated to 80° C. in an oil bath for 20 hours. The reaction mixture was diluted with ethyl acetate and filtered. The filtrate was concentrated, and the residue was triturated with ethyl acetate to give the title compound as a solid as the first batch. 1H NMR analysis showed only the trans isomer. The mother liquor was concentrated, and the residue was purified by silica gel flash column chromatography eluting with 20-50% ethyl acetate in hexane to give a second batch of the title compound. 1H NMR analysis showed indicated only trans product. 1H NMR (300 MHz, DMSO-d6) δ ppm 8.70 (dd, J=4.6, 1.6, 1H), 8.27 (dd, J=8.1, 1.6, 1H), 8.04-7.94 (m, 1H), 7.71 (dd, J=8.1, 4.6, 1H), 6.53 (d, J=16.5, 1H), 3.91 (s, 3H).

後処理

  1. customThe reaction mixture was capped
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated
  4. customthe residue was triturated with ethyl acetate

出典と根拠

ORDレコード
ord-32266a89f4664a84a88fc18d765bc1db
出典データセット
uspto-grants-2015_11
特許番号
US09187483B2

反応ノート

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