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Acrylonitrile → Dimethyl 4-(2-cyanovinyl)isophthalate

HRID 84941
Notes
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Reaction equation

HRID 84941 reaction equation
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]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 4

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

Product 1

HCID 66819156Dimethyl 4-(2-cyanovinyl)isophthalate

Reagents, catalysts & solvents 4

HCID 9811564
Bis(dibenzylideneacetone)palladium
Catalyst
HCID 8857Ethyl AcetateSolvent
HCID 312751,4-DioxaneSolvent
HCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
80 °C

Procedure

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.

Workup

  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)

Sources & evidence

ORD record
ord-5175e568045044d38ff59fe65a9dba81
Source dataset
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08846951B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes