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

HRID 716007

반응식

HRID 716007 반응식
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]

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

반응 조건

온도
80 °C

실험 절차

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).

후처리

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

출처 및 근거

ORD 기록
ord-32266a89f4664a84a88fc18d765bc1db
출처 데이터셋
uspto-grants-2015_11
특허 번호
US09187483B2

연결된 노트

불러오는 중…