Alumina-catalyzed reactions of hydroxyarenes and hydroaromatic ketones. 9. Reaction of phenol with 1-propanol

Abstract

At 250-350 °C in the presence of alumina, phenol (1) reacts with excess 1-propanol to give mainly (>90%) C'-alkylation to form mono-to penta-n-propylphenols plus some O-alkylation to form n-propyl aryl ethers. The principal component of the product mixture from 1 is 2,6-di-n-propylphenol (26-50 mol % yield). With 4-npropylphenol as substrate (instead of 1), tri-, tetra-, and penta-n-propylphenols are formed in 48-79% combined yield. On the average, only 3% of the total C3H7 groups in the product mixture are isopropyl ones. Deoxygenation is not observed. It is proposed that the principal products result from an S^-type reaction mechanism which involves nucleophilic attack (variously by C-2, C-4, C-6, or O) of an adsorbed ambident phenoxide ion onto C-l of an adsorbed n-propoxide group. n-Propylation at C-3 and C-5 of the phenol ring results from surface-catalyzed dienone-phenol rearrangement. Isopropylation may occur via a side reaction of SnI type.

Reactivity and reaction pathways in thermochemical treatment of selected lignin-like model compounds under hydrogen rich conditions

“…Moreover, the alcohol seems only to react with the phenols and pyrocatechol present in the reaction mixture since no alkylated non-hydroxy aromatic compounds are found. Indeed, such metal catalysed C-alkylation of hydroxyaromatic compounds in vapour phase or under pyrolytic conditions in the present of alcohols has been reported in the literature [23].…”

Phenol Derivatives

“…Isopropylphenols are formed by reaction of phenol or alkylphenols with propene or isopropanol in the presence of acid catalysts of the Lewis or Brønsted type or of aluminum phenolate. An extensive study of the alkylation of phenol, both with propanol and isopropanol in the presence of alumina has been published [158].…”

Synthesis and properties of novel 1,1‐difluoropropoxy‐linked liquid crystalline compounds of negative dielectric anisotropy

“…First, etherification associated with HBr elimination of the phenols (7a, 7b, 10a-10d, 13a, 13b) [6][7][8][9][10][11] with 1,1-difluoropropene derivatives (6a, 6b), using KOH as base in toluene, gave allyl ether (8a, 8b, 11a-11f, 14a-14d). Following this, catalytic hydrogenation with 5% Pd/C under a H 2 atmosphere gave the desired materials (9a, 9b, 12a-12f, 15a-15d), respectively (see schemes 1-2).…”

“…J Z-HF 52.0 Hz, 1H),6.66 (td, J59.0 Hz 4 J HF 52.0 Hz, 1H), 6.82 (td, J58.5 Hz 4 J HF 52.5 Hz, 1H) 13. C NMR d (ppm): 16.1, 22.7, 66.7, 110.7 (d, 3 J CF 53.0 Hz), 121.4 (d, 2 J CF 513.3 Hz), 124.2 (t, 3 J CF 54.8 Hz), 139.2, 142.8 (dd, 1 J CF 5247.3 Hz, 2 J CF 514.3 Hz), 148.5 (dd, 2 J CF 58.3 Hz, 3 J CF 52.5 Hz), 151.0 (dd, 1 J CF 5246.8 Hz, 2 J CF 510.8 Hz), 158.1 (t, 1 J CF 5286.1 Hz).…”