p-Toluenesulfonic acid → HCID 86623178, compound

Participants

Reaction Steps

To a 2000 ml 3 neck round bottom equipped with an overhead stirrer, dean stark trap and temperature probe was added 2,2′-dihydroxyethoxy-biphenyl (368 g, 1.34 mole, 1.0 eq.), toluene (700 g), Prostab 5198 (0.023 g), aluminum N-nitrosophenylhydroxylamine (NPAL) (0.059 g), manganese acetate (0.023 g), acrylic acid (212.7 g, 2.95 mole, 2.2 eq), p-toluene sulfonic acid (pTSA, 23.1 g, 0.13 mole, 0.1 eq.) and heated to reflux. After 2.5 hours the reaction stalled with ˜45/45 product/intermediate and 10% starting material. The reaction was treated with acrylic acid (26 g) and pTSA (5 g) and continued refluxing. No additional conversion to product was observed. Acrylic acid (50 g) and methane sulfonic acid (5 g) were added. The Dean stark trap continued to collect water. Upon running the reaction overnight the product was ˜75% product and 7% mono acrylate. The reaction was washed 3 times with sodium chloride brine (200 ml), 3 times with brine with some 1N NaOH (200 ml), 3 times with sat. sodium carbonate (200 ml), dried over MgSO4 (5 g), filtered and concentrated in vacuo to recover the product. The product (500 g) was purified by series of 3 columns eluting with 50% hexane/chloroform to recover 220 g product at 92% purity (GC) and 3 other fractions of lesser purity. The refractive index of the (i.e. uncured) monomer was determined to be 1.559.

Provenance & Evidence