Acrylonitrile → Dimethyl 4-(2-cyanovinyl)isophthalate

HRID 84941

반응식

HRID 84941 반응식
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13].[C:16](#[N:19])[CH:17]=[CH2:18].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].C(OCC)(=O)C.CCCCCC.O1CCOCC1>[C:16]([CH:17]=[CH:18][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13])#[N:19]

참가 물질

9

반응물 4

HCID 7855AcrylonitrileHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2824912Dimethyl 4-bromoisophthalateHCID 4594378Bis(cyclohexylmethyl)amine

생성물 1

HCID 66819156Dimethyl 4-(2-cyanovinyl)isophthalate

시약·촉매·용매 4

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매HCID 21226206Ethyl acetate hexane용매

반응 조건

온도
80 °C

실험 절차

A microwave vial was charged with dimethyl 4-bromoisophthalate (Example 88A, 500 mg, 1.83 mmol), acrylonitrile (117 mg, 2.20 mmol), N,N-dicyclohexylmethylamine (429 mg, 2.20 mmol), tri-tert-butylphosphine (0.11 mL, 0.11 mmol, 1.0 M in toluene), tris(dibenzylideneacetone)dipalladium(0) (50.3 mg, 0.055 mmol), and 1,4-dioxane (1.4 mL) under nitrogen. The reaction mixture was heated to 80° C. in an oil bath for 4 hours. Reaction was complete as indicated by thin layer chromatography (40% ethyl acetate/hexane). The reaction mixture was cooled to room temperature and diluted with ethyl acetate. Filtration removed HBr salts. The filtrate was concentrated. The residue was triturated with ethyl acetate/hexane (1:6) to provide dimethyl 4-(2-cyanovinyl)isophthalate as a mixture of trans and cis isomers (ratio 5.5:1) which was used in next step without further purification.

후처리

  1. customReaction
  2. temperatureThe reaction mixture was cooled to room temperature
  3. filtrationFiltration
  4. customremoved HBr salts
  5. concentrationThe filtrate was concentrated
  6. customThe residue was triturated with ethyl acetate/hexane (1:6)

출처 및 근거

ORD 기록
ord-5175e568045044d38ff59fe65a9dba81
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08846951B2

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