Polymeric Phase Transfer Catalyst Research Articles

Preparation of novel magnetic dicationic ionic liquid polymeric phase transfer catalyst and their application in nucleophilic substitution reactions of benzyl halides in water

PEG-based magnetic dicationic ionic liquid was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions of benzyl halides for the synthesis of benzyl azides and cyanides from good to excellent yields at 90°C in water. The reactions occur in water and furnish the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.

Synthesis and applications of quaternized highly branched polyacrylamide as a novel multi-site polymeric phase transfer catalyst

In current study, quaternized highly branched polyacrylamide (HBAA) was synthesized and used as an efficient multi-site polymeric phase transfer catalyst in nucleophilic substitution reactions and also in synthesis of α, β-unsaturated nitriles from reaction of acetonitrile and carbonyl compounds. The quaternized HBAA was synthesized via two steps. First, HBAA was synthesized via self-condensing vinyl polymerization of acrylamide at appropriate molar ratio of monomer to diperiodatocuprate(III). In the second step, 3-acrylamidopropyl trimethylammonium iodide was polymerized on peripheral area of the HBAA in the presence of diperiodatocuprate(III) solution again. The thermal behavior of HBAA and that of the quaternized HBAA were studied by DSC and TGA analysis. This phase transfer catalyst was easily recovered after reaction and reused several times without any loss of activity.

Kinetic study of dichlorocarbene addition to olefins via a quaternized highly branched polyacrylamide as a new multi-site phase transfer catalyst

A quaternized highly branched polyacrylamide was synthesized and used as an efficient multi-site polymeric phase transfer catalyst in dichlorocyclopropanation reaction. The quaternized highly branched polyacrylamide was synthesized via two steps. First, a highly branched polyacrylamide was synthesized via self-condensing vinyl polymerization using appropriate molar ratio of monomer to diperiodatocuprate(III) solution. In the second step, 3-acrylamidopropyltrimethylammonium iodide was polymerized on peripheral area of the highly branched polyacrylamide in the presence of diperiodatocuprate(III) solution. The thermal behavior of highly branched polyacrylamide and that of the quaternized highly branched polyacrylamide was studied by DSC and TGA analyses. Then the activity of the synthesized quaternized highly branched polyacrylamide was investigated as phase transfer catalyst in dichlorocyclopropanation of olefins in biphasic medium. To this purpose, the synthesized catalyst was used in generating dichlorocarbene from chloroform in aqueous sodium hydroxide solution which was subsequently added to olefins. This catalyst is very active and its application yields high volume of products which are obtained in relatively short time. Various factors which influence the rate of dichlorocyclopropanation reaction, such as base concentration, stirring speed, temperature and amount of catalyst, are studied and a mechanism for addition reaction of dichlorocarbene to olefins is proposed. This efficient phase transfer catalyst was reused several times without any loss of activity.

β-Cyclodextrin based polyurethane as eco-friendly polymeric phase transfer catalyst in nucleophilic substitution reactions of benzyl halides in water: An efficient route to synthesis of benzyl thiocyanates and acetates

β-Cyclodextrin, a cyclic sugar with a hydrophobic central cavity that has extensive applications in the pharmaceutical, food and biomedical industries, was polymerized with hexamethylene diisocyanate in dry dimethylformamide. Water-insoluble β-cyclodextrin-polyurethane (β-CDPU) polymer has demonstrated the ability to catalyst the nucleophilic substitution reaction of benzyl halides with thiocyanate and acetate anions in water. No evidence for the formation of by-product, for example isothiocyanate, was observed and the products were obtained in pure form without further purification. The polymeric phase transfer catalyst, easily recovered by simple filtration, shows no appreciable loss of activity when recycled several times.

PEG-SO3H as Soluble Acidic Polymeric Catalyst for Regioselective Ring Opening of Epoxides: A High-Efficient Synthetic Approach to β-Hydroxy Thiocyanates

Poly(ethylene glycol)–bound sulfonic acid, PEG-SO3H, was developed as an environmentally friendly and efficient homogeneous polymeric catalyst in organic synthesis. This polymeric phase-transfer catalyst catalyzed the regioselective ring opening of epoxides by thiocyanate ion to give thiocyanohydrins as key intermediates in agricultural and pharmaceutical chemistry in high yields.

Triphenylphosphine oxide on non-cross-linked maleimide–styrene copolymer support: As a novel stable phase transfer catalyst

Abstract A new type of linear polymeric phase transfer catalyst is readily prepared by polymerization of 3-maleimidophenyldiphenylphosphine oxide with styrene monomer in the presence of a radical initiator. It is found that this system is effective in a variety of substitution reactions even in alkaline conditions. This phase transfer catalyst is easily recovered and reused several times without the loss of activity.

Polymer-supported protic functionalized ionic liquids for nucleophilic substitution reactions: superior catalytic activity compared to other ionic resins

Three polymer-supported quaternary ammonium mesylates were synthesized for recyclable polymeric phase transfer catalysts (PTCs). Through comparison study using nucleophilic fluorination, tertiary alcohol containing polymer 3c proved to be the best catalyst with high catalytic activity and chemoselectivity. It also exhibited not only superior activity in other nucleophilic substitution reactions, such as chlorination, bromination, iodination, acetoxylation, and azidation, but also good recyclability without any loss of catalytic activity or product yield.

Facile Synthesis of 3‐Substituted‐1,2,3,4‐tetrahydropyrido‐[3,2‐d]pyrimidine‐2,4‐dione on Poly(ethylene glycol)

AbstractAn efficient and short route to synthesize pyrido[3,2‐d]pyrimidinediones was achieved using poly(ethylene glycol) as a soluble polymeric support and phase transfer catalyst. The poly(ethylene glycol) (PEG) was reacted with 2,3‐pyridinedicarboxylic anhydride to give PEG‐bound ester 1, which was transformed into corresponding PEG‐bound acyl azide 2. Then the PEG‐supported acyl azide 2 was rearranged, reacted with a series of amines and spontaneously cycled to give product 5 in 84%–88% overall yields.

Poly(diallyldimethylammonium chloride) as an Efficient Phase Transfer Catalyst in Solvent‐Free Reduction of Carbonyl Compounds with NaBH4

AbstractPoly(diallyldimethylammonium chloride) resin was used as an efficient polymeric phase transfer catalyst, which catalyzed the chemoselective reduction of aldehydes and ketones by NaBH4 to give the corresponding alcohols in high yields under solvent‐free conditions.

Cross-linked poly(diallyldimethylammonium chloride) as an efficient solid–liquid phase transfer catalyst in reduction of carbonyl compounds with sodium borohydride

Cross-linked poly(diallyldimethylammonium chloride) resin was synthesized as an efficient polymeric phase transfer catalyst. This quaternized polymer catalyzed the chemoselective reduction of aldehydes and ketones by NaBH 4 to give the corresponding alcohols in high yields under mild conditions.

Synthesis of β‐Dihydroxysulfides by Cleavage of Epoxides Using Quaternized Amino‐Functionalized Cross‐Linked Polyacrylamide as a New Polymeric Phase Transfer Catalyst.

Poly[N-(2-aminoethyl)acrylamido]trimethyl ammonium halide resin was developed as a new solid-liquid phase transfer catalyst. This quaternized polyacrylamide catalyzed regioselective ring opening of epoxide by Na 2 S to obtain bis[β -hydroxy-alkyl]sulfide in high yield under mild conditions.

Synthesis of β -Dihydroxysulfides by Cleavage of Epoxides Using Quaternized Amino-Functionalized Cross-Linked Polyacrylamide as a New Polymeric Phase Transfer Catalyst

Poly[N-(2-aminoethyl)acrylamido]trimethyl ammonium halide resin was developed as a new solid-liquid phase transfer catalyst. This quaternized polyacrylamide catalyzed regioselective ring opening of epoxide by Na 2 S to obtain bis[β -hydroxy-alkyl]sulfide in high yield under mild conditions.

Synthesis of 2-nitroalcohols from epoxides using quaternized amino functionalized cross-linked polyacrylamide as a new polymeric phase transfer catalyst

Poly[ N-(2-aminoethyl)acrylamido]trimethyl ammonium halide resin was developed as new solid–liquid phase transfer catalyst. This quaternized polyacrylamide catalyzed regioselective ring opening of epoxide by nitrite anion ( NO 2 - ) , to give 2-nitroalcohols in high yield under mild conditions.

Quaternized Amino Functionalized Cross‐Linked Polyacrylamide as a New Solid—Liquid Phase Transfer Catalyst in Reduction of Carbonyl Compounds with NaBH4.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Quaternized amino functionalized cross-linked polyacrylamide as a new solid–liquid phase transfer catalyst in reduction of carbonyl compounds with NaBH 4

Poly[ N-(2-aminoethyl)acrylamido]trimethyl ammonium chloride resin was developed as a new polymeric phase transfer catalyst. This quaternized polyacrylamide catalyzed the chemoselective reduction of aldehydes and ketones by NaBH 4 to give corresponding alcohols in high yields under mild conditions.

Synthesis of Thiocyanohydrins from Epoxides Using Quaternized Amino Functionalized Cross‐Linked Polyacrylamide as a New Solid—Liquid Phase‐Transfer Catalyst.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis of thiocyanohydrins from epoxides using quaternized amino functionalized cross-linked polyacrylamide as a new solid–liquid phase-transfer catalyst

Poly[ N-(2-aminoethyl)acrylamido]trimethyl ammonium chloride resin was developed as a new polymeric phase-transfer catalyst. This quaternized polyacrylamide catalyzed the regioselective ring opening of epoxides by thiocyanate ion to give thiocyanohydrins in high yields under mild conditions.

Synthesis of azidohydrins from epoxides using quaternized amino functionalized cross-linked polyacrylamide as a new polymeric phase-transfer catalyst

Poly[ N-(2-aminoethyl)acrylamido]trimethyl ammonium chloride resin was developed as a new polymeric phase-transfer catalyst. This quaternized polyacrylamide-catalyzed the regioselective ring opening of epoxides by azide ion to give azidohydrins in high yield under mild conditions.

Extractive pentafluorobenzylation using a polymeric phase-transfer catalyst: a convenient one-step pretreatment for gas chromatographic analysis of anionic compounds

An extractive pentafluorobenzylation procedure has been established for gas chromatographic analysis of various anionic compounds using a polymer-bound phase-transfer catalyst and pentafluorobenzyl bromide as the derivatization reagent. The efficiency of five polymer-bound catalysts was compared, and tri- n-butylmethylphosphonium bromide, polymer bound (0.75 mequ Br −/g, 200–400 mesh) was found to be the most effective. Varieties of carboxylates and phenolates in aqueous samples were readily extracted as pentafluorobenzyl (PFB) derivatives with the exception of certain compounds, such as picrate which is a weak base and sterically-hindered. The conditions for extractive derivatization for both individual and simultaneous analyses were optimized. Simultaneous derivatization could be performed under moderate conditions (i.e. at pH 6.5, 60°C). Traces of such anionic compounds, even in a relatively large volume of aqueous sample, could be efficiently captured and converted by the catalyst, and then concentrated in a small-volume organic layer as PFB derivatives.

Novel synthesis of polymeric phase transfer catalysts containingN,N-dialkylacrylamide unit and their catalytic activity

Soluble polymeric phase transfer catalysts (PTCs) containing benzyltributylphosphonium chloride moieties and polar N,N-dialkyl-acrylamide with long alkyl groups such as N,N-dipropylacrylamide, N,N-dibutylacrylamide, N,N-dihexylacrylamide, and N,N-dioctylacrylamide were prepared via two-step reactions from p-chloromethylstyrene and the corresponding N,N-dialkylacrylamide. When the obtained polymers were added, the phase transfer catalyzed reaction of benzylchloride with solid potassium acetate to proceed smoothly. The catalytic activity was strongly affected by the content of phosphonium chloride and the varieties of comonomer unit in the polymeric PTC. The polymeric PTC containing the N,N-dihexylacrylamide unit showed excellent high catalytic activity in a low polar solvent such as the mixed solvent of toluene with 70 vol % n-tridecane. Therefore, the polymer containing lipophilic long chains such as the hexyl group is desirable for polymeric PTC.