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1

Kataliza przeniesienia międzyfazowego jako nowoczesna technika w syntezie organicznej

Siewniak Agnieszka, Chrobok Anna

Wiadomości Chemiczne

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2021

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[Z] 75, 9-10

1297--1315

EN

Phase-transfer catalysis (PTC) has been already known for 60 years and has an established position both on a laboratory and industrial scale. It is an energy-saving technique, ensuring high yields and selectivity under mild conditions. PTC is successfully used, among others, in the pharmaceutical, polymer, agrochemical industries, for the production of dyes, fragrances and flavors, to name a few. Currently, the development of phase-transfer catalysis is focused mainly on the search for active catalysts as well as extending the scope of its applications. In particular, catalysts immobilized on an insoluble carrier, which can be easily separated from the reaction mixture and recycled many times, are of great interest. The growing demand for chiral compounds has resulted in the development of phase-transfer catalysts which, while retaining the advantages of conventional PTC, will allow to obtain a product with high enantiomeric excess. This work characterizes the phase-transfer catalysis and presents examples of its applications in organic synthesis.

2

Study of extraction equilibria in the reaction of alkaline hydrolysis of activated amino acid esters

Doroshkevich V. S., Baranova O. V., Shendrik A. N., Doroshkevich A. S., Lygina O. S., Lyubchyk S. B.

Chemistry-Didactics-Ecology-Metrology

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2014

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R. 19, NR 1-2

69-77

EN

Correlation between observed kinetic effects of phase-transfer catalytic reaction of the alkaline hydrolysis of 4-nitrophenyl ester of N-benzyloxycarbonylglycine-4 in the two-phase system chloroform-borate buffer pH = 10 and a content of ionic forms of catalyst was investigated. The phosphonium salts QX (X = Cl¯, Br¯, I¯) shows high catalytic reactivity. Dependence of the reaction kinetics discussed in the framework of the extraction mechanism with a competitive extraction of a nucleophile ОН¯, nucleofuge 4-NO2C6H4O¯ and anion X¯ of the phase-transfer catalyst.

PL

Zbadano korelację pomiędzy obserwowanym efektem kinetycznym przejścia fazowego katalitycznej reakcji zasadowej hydrolizy estru 4-nitrofenylowego N-benzyloksycarbonylglycyny-4 w dwufazowym układzie chloroform-bufor boranowy, pH = 10, z zawartością jonowych form katalizatora. Sole fosfoniowe QX (X = Cl¯, Br¯, I¯) wykazują wysoką aktywność katalityczną. Zależności kinetyki reakcji przeanalizowano w ramach mechanizmu ekstrakcji z konkurencyjną ekstrakcją nukleofilu ОН¯, grupą odchodzącą 4-NO2C6H4O¯ i anionem X¯ katalizatora przejścia fazowego.

3

Epoxidation of 1,5,9-cyclododecatriene with H2O2 in the presence of tungstophosphoric acid (H3PW12O40)

Wołosiak A., Lewandowski G.

Polish Journal of Chemical Technology

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2010

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Vol. 12, nr 3

40-44

EN

The influence of the technological parameters on the epoxidation of 1,5,9-cyclododecatriene (CDT) to 1,2- epoxy-5,9-cyclododecadiene (ECDD) by the phase-transfer catalysis method (PTC) in the presence of tungstophosphoric heteropolyacid (H3PW12O40) and hydrogen peroxide as the oxidizing agent has been presented. The phase-transfer catalyst was AliquatŽ 336 (methyltrioctylammonium chloride). The epoxidation of CDT to ECDD in the PTC system proceed under the relatively mild condition: low temperature, lack of solvent, short reaction time. The effect of: the mixing velocity, the molar ratio of CDT:H2O2 and H2O2:H3PW12O40, the nature of the solvent and its concentration, was studied. The most advantageous technological parameters were: the mixing rate 400 – 600 rpm, the molar ratio of CDT:H2O2= 3:1 – 1.5:1, the molar ratio of H2O2:H3PW12O40= 200:1 – 400:1, the temperature 40 – 50°C, solvent: dichloromethane or lack of the solvent, dichloromethane concentration: 10 – 50 vol%, reaction time 35 – 50 min. The application of the above-mentioned parameters allows to achieve the yield of 44 – 47% ECDD in relation to introduced CDT.

4

Synthesis and Reactions of 3-Halogeno-3-methylbenzosultams

Modrzejewska H., Wojciechowski K.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 3

585-590

EN

Halogenation of 1,3-dialkyl-2,1-benzisothiazoline 2,2-dioxides (benzosultams) with hexachloroethane or tetrabromomethane under phase-transfer catalysis conditions leads to 3-halogeno-3-methylbenzosultams. Thermal extrusion of SO2 from 3-halogeno-3-methylbenzosultams generates aza-ortho-xylylenes that undergo [1,5] hydrogen shift leading to ortho-alkylamino-a-halostyrenes, that in turn undergo reaction with anilines leading to ortho-alkylamino-a-arylaminostyrenes.

5

Removal of Water - a Factor Influencing the Synthesis of Alkynes in a Phase-Transfer Catalyzed - beta - Elimination Reaction

Zakrzewski J., Huras B., Sas A., Żelechowski K., Bombińska D.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 5

1051-1057

EN

Acetylene derivatives 4 were synthesized from the corresponding vicinal bromo compounds 2 in the phase-transfer catalyzed hydrogen bromide - beta elimination reaction using solid potassium hydroxide as a base, xylene as a solvent, and a phase-transfer catalyst. The yields of the synthesized acetylene derivatives 4 were substantially improved when water formed in the process had been removed.

6

Woda: użyteczne i nieszkodliwe dla środowiska naturalnego medium reakcyjne

Burczyk B.

Przemysł Chemiczny

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2007

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T. 86, nr 3

184-194

7

Badania nad syntezą chlorowodorku (2R,3S)-3-fenyloizoseryny

Jezierska-Zięba M., Kąkol B., Obukowicz B., Cybulski J., Fedoryński M., Szpakiewicz M.

Przemysł Chemiczny

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2007

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T. 86, nr 4

318-323

8

Highly Efficient and Regioselective Phosphorylation of Sphingolipids by Phase-Trans fer Catalysis

Szulc Z. M., Obeid L. M., Hannun Y. A., Bielawska A.

Polish Journal of Chemistry

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2007

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Vol. 81, nr 11

1899-1909

EN

Phosphorylation of D-erythro-sphingosine and its N-BOC or N-palmitoyl derivatives with trimethyl phosphite was carried out in 72–92% yield at room temperature for 20 min in a biphasic system comprised of dichloromethane/aqueous solutions of NaOH or K2CO3 using 1,2-dibromotetrachloroethane as a source of halogen and cetylpyridinium bromide as a phase-transfer catalyst. These are the first reported examples of a highly selective O- and N-phosphorylation of sphingolipids by the phase-transfer catalysis. Our studies show that the developed phosphorylation protocol works as a modular process, in which the synthetic out come is controlled by a type of the used base, catalyst and solvent system.

9

Trifluoromethylation of Carbonyl Compounds with Trifluoromethyltrimethylsilane (Ruppert Reagent) Promoted by Triphenyldifluorostannates

Borkin D., Loska R., Mąkosza M.

Polish Journal of Chemistry

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2005

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Vol. 79 / nr 7

1187-1191

EN

Nucleophilic trifluoromethylation of aromatic aldehydes and ketones with trifluoromethyltrimethylsilane is initiated with KF/n-Bu3MeN+HSO4 /Ph3SnF cocatalytic system in CH2Cl2 or with K[Ph3SnF2] in DMF.

10

Room Temperature Ionic Liqiuds-New Choline Derivatives

Pernak J., Chwała P., Syguda A.

Polish Journal of Chemistry

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2004

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Vol. 78 / nr 4

539-546

EN

New room temperature ionic liquids - choline derivatives were prepared by Menschutkin reaction with alkyl chloromethyl ethers and anion changed to bis(trifluoromethylsulfonyl) amide ion. The newly obtained butoxymethyl(2-hydroxyethyl)dimethylammonium bis(trifluoromethanesulfonyl)amide was successfully tested as a solvent for O-acylation in two-phase reaction system. The ionic liquid-catalyst system was recycled and reused.