Acrylonitrile → Dimethyl 4-(2-cyanovinyl)isophthalate

HRID 84941

反応式

HRID 84941 の反応式
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]

参加物

9

反応物 4

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

生成物 1

HCID 66819156Dimethyl 4-(2-cyanovinyl)isophthalate

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒HCID 21226206Ethyl acetate hexane溶媒

反応条件

温度
80 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-5175e568045044d38ff59fe65a9dba81
出典データセット
uspto-grants-2014_09
特許番号
US08846951B2

関連ノート

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