Selective indirect oxidation of phenol to hydroquinone and catechol

Abstract

The introduction of a hydroxyl function into phenol to give hydroquinone and catechol can be achieved in high yields by the reaction of hydrogen peroxide with alkenylphenols. These alkenylphenols are obtained by thermolysis of bisphenol A, alkylation of phenol with cyclopentadiene followed by isomerization, and alkylation of phenol with mesityl oxide followed by thermolysis to give 4-isopropenylphenol, 2-and 4-(cyclopenten-l-yl)phenol, and 2,2,4-trimethyl-l,2-chromene, respectively.

Preparation of phosphinated bisphenol from acid-fragmentation of 1,1,1-tris(4-hydroxyphenyl)ethane and its application in high-performance cyanate esters

“…In addition, literature has reported that 4-isopropenylphenol is unstable and tends to dimerize to dimmer. [10][11][12] In this case, the resulting 4-isopropynylphenol reacted with DOPO quickly, so no 4-isopropenylphenol dimmer was detected in the product. Based on this success of the model reaction, we then prepared a phosphinated bisphenol (2) from a one-pot reaction of DOPO and 1,1,1-tris(4-hydroxyphenyl)ethane in the catalysis of p-TSA.…”

“…By combing the acid-fragmentation of bisphenol [10][11][12] and conjugate addition of DOPO, [13][14][15] we first report the synthesis of a phosphinated bisphenol (2) from a one-pot reaction of DOPO and 1,1,1-tris(4-hydroxyphenyl) ethane in the catalysis of PTSA. A twostep mechanism, an acid-fragmentation of 1,1,1-tris(4-hydroxyphenyl)ethane followed by nucleophilic addition of DOPO is proposed.…”

“…[6][7][8][9] It has been reported that bisphenol A undergoes acid-or basecatalyzed fragmentation to phenol and 4-isopropenylphenol. [10][11][12] According to the fragmentation chemistry of bisphenol A and our knowledge in conjugate addition chemistry of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO), [13][14] we speculated that DOPO might react with the resulting 4-isopropenylphenol via a conjugate addition. To prove our speculation, we reacted the bisphenol A and DOPO in the catalysis p-toluenesulfonic acid as a model reaction.…”

Photodecomposition and Bioconcentration of a Bisphenol A Metabolite in Medaka, Oryzias latipes

“…8) The crude product was subjected to chromatography on a column of silica gel using a 10 : Exposure experiments in medaka and photodecomposition tests were performed using a metabolite of bisphenol A [4-methyl-2,4-bis(p-hydroxyphenyl)-pent-1-ene; MBP], the solubility limit of which is 42 mg/l of water. Three adult medaka were kept in a 2 l glass beaker at 25 ± 1°C for 4 days.…”

Synthesis and evaluation of alkoxylated-ether diols of hydroquinone with different chain-lengths as extenders in segmented polyurethanes

“…In the third step, acidic oxidation of isopropenyl group of IPP-PPC with 35 % hydrogen peroxide [30][31][32] at about 50°C led to hydroquinone monoether (OH-PPC) in 95 % yield. In the final step, OH-PPC was ethoxylated with ethylene carbonate to yield HQEP in 82 %.…”