Guaiacol allyl ether

A. Guaiacol allyl ether. A mixture of 63 g. (O.S mole) of guaia-col, 66 g. (0.55 mole) of allyl bromide,1 70 g. of anhydrous potassium carbonate (0.5 mole), and 100 ml. of dry acetone in a 500-ml. round-bottomed flask is refluxed on a steam bath for 8 hours and cooled. The mixture is diluted with 200 ml. of water and extracted with two 100-ml. portions of ether. The combined extracts are washed with two 100-ml. portions of 10% sodium hydroxide (Note 1) and dried with 50 g. of anhydrous potassium carbonate. After removal of the solvent, the residual oil (Note 2) is distilled under reduced pressure. The yield of guaiacol allyl ether boiling at 110-113°/12 mm. is 66-75 g. (80-90%). 

When this crude guaiacol allyl ether was rearranged without prior distillation, the yields of o-eugenol were about 10% lower than those obtained with the distilled ether. 

Kuntz, E., Amgoune, A., Lucas, C. and Godard, G. (2006) Palladium TPPTS catalyst in water C-allylation of phenol and guaiacol with allyl alcohol and novel isomerisation of allyl ethers of phenol and guaiacol./. Mol. Catal. A Chem., 244,124. Kuntz, E.G. (1987) Homogeneous catalysis. .. in water. Chemtech, 17, 570. Cornils, B. (1999) Bulk and fine chemicals via aqueous biphasic catalysis. /. Mol. Catal. A Chem., 143, 1. 

Kuntz E, Amgoune A, Lucas C, Godard G (2006) Palladium TPPTS catalyst in water C-allylation of phenol and guaiacol with allyl alcohol and novel isomerisation of allyl ethers of phenol and guaiacol. J Mol Catal A Chem 244 124—138... 

Preparation of 2-Allylphenol. The allyl ether is boiled in a flask under a reflux tube, the course of the rearrangement being conveniently followed by noting the refractive index at frequent intervals. When nu has risen to 1.55 (five to six hours) the rearrangement is substantially complete with the minimum formation of undesirable by-products. To separate a small amount of 2-methyldihydrobenzofuran, the product is dissolved in tivice its volume of 20% sodium hydroxide solution and extracted twice with petroleum ether (30-60°), from which the dihydro-benzofuran residue may be obtained by distillation. Ether should not be used for this extraction as it removes some of the phenol from the alkaline solution. The alkaline solution is acidified and the phenpl extracted with ether the extract is dried over calcium chloride and distilled under diminished pressure. A 73% yield of material boiling at 103-105.5°/19 mm., no 1.5445, is obtained. 2-Allylphenol is a colorless liquid, of guaiacol-like odor, with the following properties b.p. 220°/ 760 mm., 99°/12 mm., nf) 1.5453. ... 

The alkylation of benzene by propan-l-ol and AICI3 in hexane or cyclohexane has been studied over the temperature range -40 to -f-100°C by n.m.r. spectroscopy. Structures of the several products of alkylation of mesitylene with 3,5-di-t-butyl-4-hydroxybenzyl alcohol and of resorcinol and its methyl ethers with a-butylbenzyl alcohol plus orthophosphoric acid have been elucidated. Allylation of guaiacol by allyl alcohol and an acid catalyst is... 

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