Toluene → Dimethyl 2'-cyano-4'-methylbiphenyl-3,5-dicarboxylate

HRID 1845194Notes

Reaction equation

HRID 1845194 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[CH:5]=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[CH3:16][C:17]1[CH:18]=[CH:19][C:20](B2OC(C)(C)C(C)(C)O2)=[C:21]([CH:24]=1)[C:22]#[N:23].C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>CCOC(C)=O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O.C(O)C>[C:22]([C:21]1[CH:24]=[C:17]([CH3:16])[CH:18]=[CH:19][C:20]=1[C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[CH:5]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:11]=1)#[N:23]

Participants

9

Reactant 4

HCID 1140TolueneHCID 10796Cesium carbonateHCID 1039541,3-Benzenedicarboxylic acid, 5-bromo-, 1,3-dimethyl esterHCID 584073295-Methyl-2-(tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile

Product 1

HCID 58188054Dimethyl 2'-cyano-4'-methylbiphenyl-3,5-dicarboxylate

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A Parr pressure reactor was charged with dimethyl 5-bromoisophthalate (1.3 g, 4.8 mmol), 5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (2.0 g, 5.9 mmol), toluene (25 mL), ethanol (5 mL), cesium carbonate (1.7 g, 5.2 mmol), and water (2.5 mL). The mixture was degassed and purged with nitrogen several times before tetrakis(triphenylphosphine)-palladium(0) (280 mg, 0.24 mmol) was added. The tube was sealed and the mixture was heated at 90° C. overnight. After cooling, the mixture was diluted with EtOAc (200 mL), washed with brine, dried over Na2SO4, and concentrated. The residue was purified via flash chromatography to afford the desired product as a white solid. LC-MS: 310.5 [M+1]+; 1H NMR (400 MHz, CDCl3): 8.75 (s, 1H), 8.39 (d, J=1.6 Hz, 2H), 7.61 (s, 1H), 7.49 (dd, J=1.1, 8.5 Hz, 1H), 7.43 (d, J=7.9 Hz, 1H), 3.98 (s, 6H), 2.46 (s, 3H).

Workup

  1. customThe mixture was degassed
  2. additionwas added
  3. customThe tube was sealed
  4. temperatureAfter cooling
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe residue was purified via flash chromatography

Sources & evidence

ORD record
ord-82d9b3c867e242f0bb4f5bb54df0a51c
Source dataset
uspto-grants-2015_02
Patent number
US08946439B2

Reaction notes

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