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1

Ditlenek węgla w syntezie organicznej

Burczyk B.

Wiadomości Chemiczne

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2013

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[Z] 67, 1-2

1--53

EN

Carbon dioxide is an abundant, cheap, almost nontoxic, thermodynamically stable, inert electrophile. Exploitation of CO 2 as a chemical feedstock, although will almost certainly not reduce its atmospheric concentration significantly, aims to generate high-value products and more-efficient processes. In recent years efficient transition-metal complexes have been used to perform homogeneously catalyzed transformations of CO 2 . This paper presents an overview of available catalytic routes for the synthesis of carboxylic acids, lactones, urea and carbamates, linear and cyclic carbonates as well as polycarbonates. Reduction processes of CO 2 are shortly men - tioned as well. C arboxylic acids have been synthesized via : (i) carboxylation of organolithium, organomagnesium (Scheme 2 [35]), organoboron (Scheme 3 [40 -42]), organozinc (Scheme 4 [43, 44]) and organotin (Scheme 5 [45, 46]) compounds; (ii) oxidative cycloaddition of CO 2 to olefins and alkynes (Scheme 6 -10 [47 -50, 57]) catalyzed by Ni(0)-complexes; (iii) transition-metal catalyzed reductive hydrocarboxylation of unsaturated compounds (Scheme 11, 12 [64 -67]); (iv) carboxylation of C-H bond (Scheme 13 [69 -71]). Telomerization of dienes, for instance 1,3-butadiene, and CO 2 in the presence of Ni(II) and Pd(II) complexes leads to lactones and esters of carboxylic acids (Scheme 14, 15 [73 -79]). Nucleophilic ammonia, primary and secondary amines react with CO 2 to give, respectively, urea and carbamic acid esters - carbamates and isocyanates (Scheme 16 -18 [94, 95]), thus eliminating the use of phosgene in their synthesis. CO 2 reacts with alcohols, diols and epoxides in the presence of transition-metal complexes (Fig. 2) and the reaction products are: linear carbonates (Scheme 20, 21 [110 -118]), cyclic carbonates (Scheme 22 -24 [153 -170]) and polycarbonates (Scheme 25, 26, Fig. 3, Tab. 1 [179 -186]). Finally, hydrogenation of CO 2 , leading to the formation of CO, HCOOH, CH 3 OH, CH 4 , C 2 H 6 and C 2 H 4 (Scheme 27), as well as electrochemical and photochemical reductions in the pre - sence of homogeneous and heterogeneous catalysts have been shortly reviewed.

2

Biorafinerie: ile w nich chemii?

Burczyk B.

Wiadomości Chemiczne

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2009

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[Z] 63, 9-10

739-776

EN

A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. The biorefinery concept is analogous to today’s petroleum refineries, which produce multiple fuels and products from petroleum [12]. Three biorefinery systems are distinguished in research and development [11, 13]: the „whole-crop biorefinery”, the „lignocellulosic biorefinery” and the „green biorefinery”. Moreover, a concept of „two platform biorefinery” emerged [14], which includes the sugar platform as a basis for (bio) chemical conversion of biomass and the syngas (thermochemical) platform which convert biomass into synthesis gas. This review focuses on the recent developments of basic biorefinery technologies. The whole-crop biorefinery (Figure 1) produces chemicals from sugars by biochemical (Scheme 1) and chemical (Schemes 2–11) transformations, of which twelve compounds, selected by US National Renewable Energy Laboratory (NREL) [14] are classified as „block (or platform) chemicals” with the potential to be transformed into new families („trees”) of valuable substances. These compounds are: 1,4-diacids (succinic, fumaric, malic), 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, aspartic acid , glutamic acid, glucaric acid, itaconic acid, levulinic acid, 3-hydroxybutyrolactone, glycerol, sorbitol, and xylitol/arabinitol. The lignocellulosic biorefinery (Figure 2) uses biomass consisting of cellulose, hemicelluloses and lignin – an abundant and cheap feedstock. Among the potential products of the „sugar platform” are: cellulosic ethanol and hydrogen obtained by biochemical routs, and furfural, 5-hydroxymethylfurfural, the platform chemicals, (Schemes 3–11), obtained by chemical synthesis. The „syngas platform” covers three basic processes: aqueous – phase reforming of sugar polyols [109–111, 113–115] and glycerol [116–118], fast pyrolysis of biomass [121–128] and gasification of biomass [121–125]. Aqueous – phase reforming of glucose and sorbitol produces hydrogen, whereas integrated with catalytic cascade processes allows to produce liquid biofuels, i.e., branched hydrocarbons and aromatic compounds used in gasoline or longer chain linear hydrocarbons in diesel and jet fuels. Fast pyrolysis produces bio-oil that can be upgraded to transportation fuels. Synthesis gas is produced in gasification processes and may be converted into methanol or liquid hydrocarbons (so-called synthetic „Biomass–To–Liquid”, BTL-fuel) [131–133]. Finally, green biorefinery (Figure 3) uses green (wet) biomass rich in juice and oil to obtain food and non food goods, and from the latter a huge number of chemicals „produced” by Nature, i.e., by the vast diversity of plant.

3

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

4

Zielona chemia - zrównoważona chemia: perspektywy rozwoju

Burczyk B.

Przemysł Chemiczny

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2005

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T. 84, nr 3

162-166

PL

Omówiono filozofię zielonej i zrównoważonej chemii, wpisujących się w paradygmat zrównoważonego rozwoju cywilizacji. Podano definicje pojęć: „zielona chemia”, „zielona inżynieria”, „zrównoważona chemia” oraz podkreślono ważność zawartych w nich propozycji dla dalszego rozwoju przemysłu chemicznego. Zwrócono uwagę na próby określenia miar ilościowych zrównoważonego procesu chemicznego oraz na aspekty społeczne z nim związane.

EN

The philosophy underlying the green and sustainable chemistry and EPA’s definitions of green chemistry, green engineering, and sustainable chemistry are described, quant. measures of sustainable chemistry are presented and societal aspects are discussed. 67 refs.

5

Zielona chemia : zadania, cele, przykłady osiągnięć

Burczyk B.

Wiadomości Chemiczne

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2002

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[Z] 56, 9-10

709-770

EN

Green chemistry is the design, development, and implementation of chemical processes or products to reduce or eliminate the use and generation of substances hazardous to human health and the environment : Its aim is to combine technological and economic progress with the safeguarding of the environment, which is one of the challenges of the new millennium. To help to achieve this goal, a set of twelve principles of green chemistry was formulated by Anastas and Warner. These principles apply to a whole chemical process and to its main stages, which are: starting materials (or feedstock), reaction types and reagents, solvents and reaction conditions, and chemical products . This review only covers some of the important efforts and achievements of green chemistry. In Section 3.1 some saccharide- based syntheses are presented. Both simple sugars (glucose, lactose), and polymeric saccharides, as well as biomass have been successfully transformed into valuable chemicals. In Section 3.2, new reaction types fulfilling the atom economy principle formulated by Trost re described. The focus is on new oxidation reactions of olefins using clean oxidants: hydrogen peroxide and non-toxic, water-soluble iron catalysts, and oxygen. New possibilities of replacing toxic hydrogen cyanide and phosgene with safer reagents (e.g., dimethyl carbonate) were another topic of this Section. Section 3.3 deals with new reaction media. Water emerged as a non-toxic, environmentally benign and cheap solvent for many organic reactions, as it has several advantages: water soluble substrates (e.g., carbohydrates) can be used directly, the aqueous catalyst solution can be recycled easily, and no inert gas atmosphere is needed. The discovery of water soluble transition metal complexes made it possible to use aqueous/organic biphasic systems which have benefits in catalyst separation and recycling. Such a system has been used, for instance, in the industrial propylene hydroformylation process. Many other reactions performed in biphasic systems were reported. Water soluble rare earth trifluoromethane sulfonates have been shown to be strong Lewis acids . Supercritical fluids have been used as new reaction media; they posses a unique combination of gas- and liquid- like properties. Supercritical carbon dioxide (scCO2) and supercritical water (scH2O) were mostly exploited. New polymerization processes in scCO2 were proposed and new surfactants for scCO2 were discovered . Promising possibilities of performing oxidation reactions in scH2O were reported, as many organic compounds and oxygen are soluble in scH2O . Ionic liquids, which are characterized by a lack of measurable vapour pressure, constitute another group of neoteric solvents. They can serve both as powerful solvents (e.g., in extraction processes) and as reaction media with catalytic properties. The last Section (3.4) deals with chemical products safe for humans and for the environment. The focus is on polymers, pesticides and surfactants that are produced in a large volume. New "metallocene polyolefins" and water soluble, biodegradable polymers seem to fulfil this requirement. Selective pesticides, non-toxic to mammals, birds, and beneficial insects have been implemented, among them biopesticides. Biodegradable "sugar surfactants" and chemodegradable, acetal-type surfactants have been synthesized and some of them are already industrially produced. The review ends with some remarks on the perspectives of green chemistry in the near future (Section 4). In this context, the need for far-reaching educational initiative to promote the scientific principles of green chemistry, which were developed and implemented to the benefit of society, is stressed .

6

Właściwości antybakteryjne i biologiczny rozkład niejonowych surfaktantów typu aldonamidów

Maliszewska I., Wilk K. A., Burczyk B., Syper L.

Prace Naukowe Instytutu Technologii Organicznej i Tworzyw Sztucznych Politechniki Wrocławskiej. Konferencje

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2000

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Vol. 48, nr 22

217-220

PL

W prezentowanej pracy metodą szeregu rozcieńczeń na podłożach stałych określono antybakteryjna i antygrzybową aktywność nowej grupy cukrowych surfaktantów typu gemini (bliźniaczych): N,N'-bisalkilo-N,N'-bis[3-(aldonoamido)propylo]alkilenodiamin. Okazało się, że związki te nie wpływają na wzrost bakterii gramujemnych i grzybów. Bardziej wrażliwe na ich działanie są bakterie gramdodatnie. Ponadto w warunkach tzw. Closed Bottle Test wszystkie testowane surfaktanty w ciągu 28 dni ulegają biodegradacji. Przeprowadzone doświadczenia wykazały, że badaną grupę surfaktantów można zaliczyć do tzw. "zielonych surfaktantów", a więc takich, które są przyjazne naturalnemu środowisku.

EN

Gemini N,N'-bisalkyl-N,N'-bis[3-(aldonamido)propyl]alkylendiamines were studied for their antimicrobial activity and biodegradability. All tested surfactants were practically non-toxic to gram-negative bacteria and fungi. But these compounds had a broad spectrum of antimicrobial activity against gram-positive bacteria. All studied surfactants were biodegradable in the Closed Bottle Test inoculated with activated sludge. Biological properties showed that this class of compounds fulfils all requirements needed for environmental acceptance.

7

Charakterystyka mikrośrodowiska micel diastereoizometrycznych surfaktantów anionowych

Piasecki A., Wilk K. A., Burczyk B., Matuszewska B., Sokołowski A.

Prace Naukowe Instytutu Technologii Organicznej i Tworzyw Sztucznych Politechniki Wrocławskiej. Konferencje

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2000

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Vol. 48, nr 22

133-136

PL

Przeprowadzono badania wpływu zmiany konfiguracji grupy siarczanowej przy atomie węgla C-5 pierścienia dioksanu (cis- i trans-1-3) na zdolność agregacji micelarnej. Badane diastereoizomery, podatne na hydrolityczny rozpad, stanowią nowy typ chemodegradowalnych surfaktantów, o zdolnościach agregacyjnych analogicznych do SDS.

EN

The results presented in this paper concerning micellar aggregation of cis- and trans~sodium(2n-alkyl-1,3- dioxan-5-yl)sulfates l--3 constitude the first observation that the change of head group configuration at the C-5 carbon atom of the 1,3-dioxane moiety from axial position in the cis-1-3 isomers to equatorial position in the trans 1-3 isomers of the described surfactants introduces diastereomeric differentiation in aggregation phenomena in water. Because the studied acetal-type isomers contain a 1,3-dioxane unit, they can appear as a new acid-hydrolyzable type of chemodegradable surfactants, which are analogous to sodium dodecyl sulfate in terms of micellar aggregation characteristics.