1-METHYL-2-(DIPHENYLPHOSPHINO)TEREPHTHA& synthesis

Yield:361154-31-6 94%

Reaction Conditions:

with palladium diacetate;triethylamine in methanol; for 10 h;Inert atmosphere;Reflux;

Steps:

4 2.1.4 Synthesis of 1-methyl 2-(diphenylphosphino)terephthalate 3

A 250 ml flask was flame dried and charged with argon. 3-iodo-4-(methoxycarbonyl) benzoic acid (1.86 g, 5 mmol, 1 eq.), Pd(OAc)₂ (112 mg, 0.5 mmol, 0.1 eq) and TEA (1.42 mL, 10 mmol, 2 eq) were then solved in 50 ml dry methanol. After that (0.87 ml, 5 mmol, 1 eq.) diphenylphosphine were added with a syringe and then the mixture was boiled under reflux for 10 h. The solution was then concentrated under reduced pressure, the residue were then solved in 150 ml DCM and washed with 150 ml water. The organic phase was washed with 60 ml 1 M HCl and then was concentrated under reduced pressure. The crude product was then washed with a cooled 4:1 MeOH:H₂O mixture and purified by column chromatography over silica gel and a 7:1 mixture of CHCl₃:MeOH. This gives 1.73 g of a yellow solid (4.7 mmol, 94%). ¹H-NMR (300 MHz, CDCl₃): δ = 3.75 (s, 3H, CH₃), 7.32 (m, 10H, CH), 7.66 (s, 1H, CH), 8.00 (s, 2H, CH). ¹³C-NMR (100.63 MHz, CDCl₃): δ = 52.82, 129.41, 130.52, 131.15, 132.44, 138.35, 140.23, 142.58, 166.53, 169.07. ³¹P NMR (162.02 MHz, CDCl₃): δ = -4.27. ESI-MS: M_calculated = 365.0864; M_measured = 365.0918 [M+H]⁺

References:

Sallouh, Omar;Weberskirch, Ralf [Polymer,2016,vol. 86,p. 189 - 196]