Nitrogen → methyl (2E)-3-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-2-propenoate

HRID 1496920

Reaction equation

HRID 1496920 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[C:10]([O:12][CH3:13])=[O:11])=[CH:4][CH:3]=1.[F:14][C:15]([F:31])([F:30])[O:16][C:17]1[CH:22]=[CH:21][C:20](C2C=CC(O)=CC=2)=[CH:19][CH:18]=1.C([O-])([O-])=O.[K+].[K+].N#N>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[F:14][C:15]([F:30])([F:31])[O:16][C:17]1[CH:22]=[CH:21][C:20]([C:2]2[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[C:10]([O:12][CH3:13])=[O:11])=[CH:4][CH:3]=2)=[CH:19][CH:18]=1

Participants

7

Reactant 4

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 816774Methyl 4-bromocinnamateHCID 120087344-(4-Trifluoromethoxyphenyl)phenol

Product 1

HCID 54757818methyl (2E)-3-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-2-propenoateYield 85%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of methyl (E)-3-(4-bromophenyl)-2-propenoate (99) (0.500 g, 2.07 mmol) and 4-(trifluoromethoxy)phenylboronic acid (44) (0.612 g, 2.97 mmol) in dioxane (40 mL) and aqueous K2CO3 (2M, 10 mL, 20 mmol) was purged with N2. Pd(dppf)Cl2 (0.050 g, 0.06 mmol) was added and the solution was refluxed under N2 for 1 h. The dioxane was removed and the residue was extracted with EtOAc, the organic fraction was dried and the solvent was removed. Column chromatography of the residue on silica gel using gradient elution (hexanes to CH2Cl2) gave methyl (2E)-3-[4′-(trifluoromethoxy)[1,1′-biphenyl]-4-yl]-2-propenoate (100) (0.567 g, 85%) as a white solid: mp 98-100° C.; 1H NMR (CDCl3) δ 7.73 (d, J=16.0 Hz, 1H), 7.56-7.63 (m, 6H), 7.30 (dd, J=8.8, 0.9 Hz, 2H), 6.48 (d, J=16.0 Hz, 1H), 3.82 (s, 3H). APCI MS m/z 323 [M+H]+.

Workup

  1. temperaturethe solution was refluxed under N2 for 1 h
  2. customThe dioxane was removed
  3. extractionthe residue was extracted with EtOAc
  4. customthe organic fraction was dried
  5. customthe solvent was removed
  6. washColumn chromatography of the residue on silica gel using gradient elution (hexanes to CH2Cl2)

Sources & evidence

ORD record
ord-af23c11d57c3404a979a89cdabf7813c
Source dataset
uspto-grants-2015_12
Patent number
US09198913B2

Linked notes

Loading…