Solid‐Phase Organic Synthesis of Aryl Vinyl Ethers Using Sulfone‐Linking Strategy

Abstract

A novel facile solid‐phase organic synthesis of aryl vinyl ethers by reaction of polystyrene‐supported 2‐phenylsulfonylethanol with phenols under Mitsunobu conditions and subsequent elimination reaction with DBU has been developed. The advantages of this method include straightforward operation, good yield and high purity of the products. Alternatively, a typical example of Suzuki coupling reaction on‐resin was further applied to prepare 4‐phenylphenyl vinyl ether for extending this method.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene

“…IR spectrum, ν, cm -1 : 1640 (C=C). 1 Н, 13 С NMR spectra differ from those described in [33,34]. 1 1,4-Divinyloxybenzene (4).…”

“…Divinyl ethers 4 and 5 were obtained similarly from dihydric phenols (50 mmol) and acetylene. [36]); mp 31-32°С [33,34,51]. IR spectrum, ν, cm -1 : 1640 (C=C).…”

“…New methods of aryl vinyl ethers production are under development, among which the following are worth considering: catalytic reaction of phenols with various vinyl equivalents, e.g., vinyl halides [25, 26], vinylboronic acids [27, 28], tetravinyl-and tributyl-(vinyl)tin [29], vinyl esters of carboxylic acids [21, 30], and also the synthesis of aryl vinyl ethers from 2-phenylselenyl-ethanol [31-33] or 2-phenylsulfonylethanol [34] and phenols at treating with Mitsunobu reagent (diethyl ether of azodicarboxylic acidtriphenylphosphine). Recently a new two-stage method was patented of the production of aromatic vinyl ethers in a low yield (10-38%) involving vinylation of 2-aryloxyethanols (100 о С, 3-6 h, acetylene pressure 1.4 at, KОН-DMSO) with the formation of the corresponding 2-aryloxyethyl vinyl ethers followed by heating of the latter (130-140 о С, 6-10 h, DMSO) in the presence of double molar excess of KОН [35].The classic synthesis method of aryl vinyl ether through direct phenol vinylation with acetylene under the basic catalysis conditions not only conserves its importance but possesses obvious advantages before the mentioned procedures [21,[25][26][27][28][29][30][31][32][33][34][35] since it is atomeconomical, one-stage, and is based on a raw material of a large-scale production. Phenols add to acetylene in the presence of KОН at a high pressure (30-50 at) and a high temperature (180-200 о С) [2,[36][37][38][39][40].…”

“…New methods of aryl vinyl ethers production are under development, among which the following are worth considering: catalytic reaction of phenols with various vinyl equivalents, e.g., vinyl halides [25,26], vinylboronic acids [27,28], tetravinyl-and tributyl-(vinyl)tin [29], vinyl esters of carboxylic acids [21,30], and also the synthesis of aryl vinyl ethers from 2-phenylselenyl-ethanol [31][32][33] or 2-phenylsulfonylethanol [34] and phenols at treating with Mitsunobu reagent (diethyl ether of azodicarboxylic acidtriphenylphosphine). Recently a new two-stage method was patented of the production of aromatic vinyl ethers in a low yield (10-38%) involving vinylation of 2-aryloxyethanols (100 о С, 3-6 h, acetylene pressure 1.4 at, KОН-DMSO) with the formation of the corresponding 2-aryloxyethyl vinyl ethers followed by heating of the latter (130-140 о С, 6-10 h, DMSO) in the presence of double molar excess of KОН [35].…”

“…The classic synthesis method of aryl vinyl ether through direct phenol vinylation with acetylene under the basic catalysis conditions not only conserves its importance but possesses obvious advantages before the mentioned procedures [21,[25][26][27][28][29][30][31][32][33][34][35] since it is atomeconomical, one-stage, and is based on a raw material of a large-scale production. Phenols add to acetylene in the presence of KОН at a high pressure (30-50 at) and a high temperature (180-200 о С) [2,[36][37][38][39][40].…”