Propiolic Acid → (3-methoxy-phenyl)-propynoic acid methyl ester

HRID 227923Notes

Reaction equation

HRID 227923 reaction equation
Br[C:2]1[CH:3]=[C:4]([O:8][CH3:9])[CH:5]=[CH:6][CH:7]=1.[C:10]([OH:14])(=[O:13])[C:11]#[CH:12].[CH:15]1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(S([O-])(=O)=O)=CC=2C(C)C)CCCCC1.[Na+].C([O-])([O-])=O.[Cs+].[Cs+]>C(#N)C.O>[CH3:15][O:13][C:10](=[O:14])[C:11]#[C:12][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][CH3:9])[CH:3]=1

Participants

7

Reactant 4

HCID 10110Propiolic AcidHCID 10796Cesium carbonateHCID 169713-BromoanisoleHCID 23674066Sodium 2'-(dicyclohexylphosphino)-2,6-diisopropyl-[1,1'-biphenyl]-4-sulfonate

Product 1

HCID 11665545(3-methoxy-phenyl)-propynoic acid methyl esterYield 925.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

The general procedure described in Example 27 was used with 3-bromoanisole (0.063 mL, 0.50 mmol), propiolic acid (added at 0° C.) (0.050 mL, 0.65 mmol), PdCl2(CH3CN)2 (3.2 mg, 0.0125 mmol, 1.25 mol %), sodium 2′-(dicyclohexyl-phosphanyl)-2,6-diisopropyl-biphenyl-4-sulfonate (20.0 mg, 0.0375 mmol, 3.75 mol %), Cs2CO3 (650 mg, 2.00 mmol), water (1.0 mL), acetonitrile (1.0 mL), 12 h, 60° C. The product was isolated as a colorless oil (66 mg, 69%). 1H NMR (400 MHz, CDCl3) δ: 7.28 (t, 1H, J=7.6 Hz, 8.4 Hz), 7.17 (dt, 1H, J=1.2 Hz, 7.6 Hz), 7.09 (m, 1H), 7.00 (qd, 1H, J=1.2 Hz, 2.4 Hz, 8.4 Hz), 3.84 (s, 3H), 3.80 (s, 3H). 13C NMR (125 MHz, CDCl3) δ: 159.4, 154.6, 129.9, 125.6, 120.5, 117.7, 117.6, 86.6, 80.2, 55.5, 52.9.

Sources & evidence

ORD record
ord-11fd3d566e22437fbc3217029982ee0d
Source dataset
uspto-grants-2009_07
Patent number
US07560596B2

Reaction notes

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