Global Antifungal Profile Optimization of Chlorophenyl Derivatives against Botrytis cinerea and Colletotrichum gloeosporioides

Twenty-two aromatic derivatives bearing a chlorine atom and a different chain in the para or meta position were prepared and evaluated for their in vitro antifungal activity against the phytopathogenic fungi Botrytis cinerea and Colletotrichum gloeosporioides. The results showed that maximum inhibition of the growth of these fungi was exhibited for enantiomers S and R of 1-(40-chlorophenyl)- 2-phenylethanol (3 and 4). Furthermore, their antifungal activity showed a clear structure-activity relationship (SAR) trend confirming the importance of the benzyl hydroxyl group in the inhibitory mechanism of the compounds studied. Additionally, a multiobjective optimization study of the global antifungal profile of chlorophenyl derivatives was conducted in order to establish a rational strategy for the filtering of new fungicide candidates from combinatorial libraries. The MOOPDESIRE methodology was used for this purpose providing reliable ranking models that can be used later

Catalytic performance of Rh/SiO2 in glycerol reaction under hydrogen

Glycerol is a main byproduct in the biodiesel production process, and the effective utilization of glycerol can contribute to biodiesel promotion. One of the possible methods is the catalytic conversion of glycerol to valuable chemicals, and this can also agree with the concept of green chemistry in terms of the utilization of renewable resources. Catalytic performance of supported metal catalysts (metal: Rh, Ru, Pt, Pd support: active carbon, SiO2, Al2O3) was evaluated in the reaction of glycerol aqueous solution under H2. It is found that Rh/SiO2 exhibited higher activity and higher selectivity to hydrogenolysis products such as propanediols and propanols than Ru/C catalysts at low temperature (393 K). We also investigated the additive effect of ion-exchange resin (Amberlyst). Regarding the reaction route in the reaction of glycerol, it is suggested that the consecutive hydrogenolysis of propanediols to propanols on Rh/SiO2 can proceed via 1,2-propanediol, while it can proceed on Ru/C via 1,3-propanediol

Fenntartható fluoros kémia = Sustainable fluorous chemistry

(1) A „zöldebb” fluoros kémia kialakítása érdekében számos trifluormetil-csoportban gazdag reagens hatékony szintézisét dolgoztuk ki, melyek könnyen hozzáférhető szerves fluorvegyületek hasznosítására és várhatóan nagyobb környezeti lebomlási készségére hívják fel a figyelmet. (2) Eljárásokat dolgoztunk ki 3-perfluoralkil-propanol és 3-perfluoralkil-propén típusú intermedierek előállítására, illetve a köztitermékként megjelenő ún. jódhidrinek sokoldalú preparatív átalakítására. (3) Új típusú fluoros ionos folyadékokat, imidazólium-sókat és más intermediereket állítottunk elő. (4) Orosz fejlesztésű kompozit anyagokat (FUKM, FUKM-M és FUKM-MT) kémiai reagensként, illetve átmenetifém katalizátor (Pd/FUKM) hordozóként alkalmaztunk. (5) Tanulmányoztuk a Hiyama- és a Heck-kapcsolási reakciók mechanizmusát és szintetikus alkalmazhatóságát. (6) CF3I reagnest S-alkilezőszerként alkalmaztuk (7) Prof. Bühlmann al együttműködve fluoros ionofórokat és elektrokémiai szenzorokat készítettünk. (8) Azonosítottuk egy új potenciális fluorátvivő reagens molekulaszerkezeti feltételeit, melynek segítségével lehetőségünk nyílik a fluoros kémiából (fluortartalmú modulok) a fluorkémiába (szén-fluor kötesek kialakítása) átlépnünk. Ez lehetőséget ad a gyógyszerkémia számára fontos egy, kettő, vagy három fluoratomot tartalmazó vegyületek hatékony előállításához. Több közlemény csak a kövtekező évben fog megjelenni, kérem az értékelésnél ezt vegyék figyelembe. | (1) For Greener Fluorous Chemistry we developed the synthesis of several reagents from easily accessible precursor, reach in CF3-goups, which expected to have less impact and shorter environmental half-lives. (2) Novel methods for the synthesis of 3-perfluoroalkyl-propanols and –propenes were disclosed along with the uses of their synthetic intermediates. (3) New types of fluorous ionic liquids were synthesised based on imidazolium-salts. (4) Carbon-fluorinated carbon composite materials of Russian origin were applied as chemical reagents and transition metal catalyst support material (e.g. Pd/FUKM) . (5) Hiyama- and Heck-reactions with fluorous substrates were studied for a synthetic and mechanistic point of view. (6) Trifluoroiodomethane was used for improved S-alkylating processes. (7) Fluorous ionophores and electrochemical sensors were designed for the first time in co-operation with Prof. Bühlmann. (8) The structural requirements for a potential new fluorine-transfer reagent were identified and a Patentable process designed. This will allow the introduction of one, two or three fluorine atoms into target pharmaceutical molecules, and allow a shift from the fluorous to the fluorine chemistry (i.e. from F-building blocks to create C-F bonds). Please consider that some more publications are expected to appear only in the next year

Gaschromatographische Ameisensäurebestimmung in wäßrigen Lösungen

Ameisensäure kann neben Essigsäure in wäßrigen Lösungen als n-Propylformiat gc in einer Grenzkonzentration von 2,4 ppm [w/v] bei einer Standardabweichung von 3,8% auf PAeG 4000/Chromosorb G bestimmt werden. Große Mengen anorganischer Ionen (S04 2-, S03 2-, J-) stören nicht

Királis, fluoros fázisban oldható homogén katalizátor prekurzor ligandumok szintézise és alkalmazása = Synthesis and application of chiral fluorous phase soluble ligands for catalysts

Mitsunobu-reakcióban pro-nukleofilként viselkedő fluoros vegyületek [(CF3)3COH, (CF3)2C(OH)2, perfluoropinakol, CF3SO2NH2] és perfluoralkil-propanolok [CnF2n+1(CH2)3OH] reakciójával fluorofil O- és N-alkilezett származékokat állítottunk elő jó termeléssel. Kidolgoztuk egy új típusú fluorofil szerkezeti részlet beépítését [(CF3)3CO], ami nagyfokú kémiai stabilitással rendelkezik és nagymértékű fluorofilitást biztosít. Preparatív méretekben (50-500 g) kidolgoztuk fluorofil reagensek szintézisét (éterek, aminok, jódhidrinek, alkoholok, alkének) egyszerű kiindulási anyagokból. A termékek tiszta állapotban történő kinyerésére fluoros extrakciót, szilárd fluoros - szerves folyadék szűrést és vízgőzdesztillációt alkalmaztunk. Fluoros propének esetében piridin segítségével oldószergőz-desztillációval sikerült a tisztítást elvégezni. Előállítottuk az optikailag aktív feniletilamin fluoros származékait. A szabad bázisok és hidrokloridjaik oldhatóságát tíz különböző oldószerben vizsgáltuk. Egy új módszert alkalmaztunk egy szulfoxid-dikarbonsav fluoros királis bázissal történő reszolválására vizes közegben. Az előállított molekulák szelektív fizikai tulajdonságait vizsgáltuk (olvadáspont, forráspont, fluoros megoszlási hányados) és kvalitatív következtetéseket vontunk le a szerkezet és a makroszkópikus tulajdonságok között. | The Mitsunobu reaction of pro-nucleophiles (CF3)3COH, (CF3)2C(OH)2, perfluoropinacol and CF3SO2NH2 with CnF2n+1(CH2)3OH alcohols resulted in the high yield formation of the appropriate fluorophilic O- and N-alkylated products. The novel bulky fluorous ponytail (CF3)3CO displays high acidic stability and increases fluorousness almost as much as the classical straight-chain C8F17(CH2)3 ponytail. Fluorophilic reagents (ethers, amines, iodohydrines, alcohols, alkenes) were prepared in preparative scale in good yields starting from commercially available chemicals. To achieve ideal separations, products were transferred to orthogonal phases relative to the other reaction components using fluorous extraction, fluorous solid?organic liquid filtration, or steam-distillation. Fluorous propenes were effectively isolated by co-distillation with pyridine. Fluorous chiral amine derivatives of phenylethylamin were obtained. The solubility patterns of these novel chiral amines and their hydrochlorides were qualitatively described for a broad spectrum of solvents. A novel method for the resolution of enantiomers was disclosed, which involves the use a half-equivalent of the selected resolving agent in water. Selected physical properties including melting and boiling point, together with fluorous partition coefficients of compounds were determined and the figures obtained were qualitatively analyzed

A screening method for ranking chemicals by their fate and behaviour in the environment and potential toxic effects in humans following non-occupational exposure

A large number of chemicals are released intentionally or unintentionally into the environment each year. These include thousands of substances that are currently listed worldwide and several hundred new substances added annually (Mücke et al., 1986). When these compounds are used, they can reach microorganisms, plants, animals and man either in their original state or in the form of reaction and degradation products via air, water, soil or foodstuffs. Hence environmental chemicals can occur in practically all environmental compartments and ecosystems. It is not feasible to conduct assessments of human exposure and possible associated health effects for all chemicals. Even if the necessary resources were available, reliable data for a quantitative evaluation are likely to be absent in most cases. This has led to the development of schemes for prioritising compounds likely to be of environmental significance. Such schemes can be used to direct future research efforts towards the prioritised compounds. This study was commissioned by the Department of Health (DH) as part of a broader research activity that aims to identify key priority chemicals of concern to human health at routine levels of environmental exposure. The main pathways of human exposure are shown in Figure 1.1. A review of the principal prioritisation schemes used by different organisations to assess the significance of chemical release into the environment has been conducted by the MRC Institute for Environment and Health (IEH, 2003). This review showed that the approaches used by different organisations vary widely, depending on the initial reasons for which the schemes were developed. The basic information presented in the review was used to develop a simple screening method for ranking chemicals. The model used in this prioritisation scheme is outlined in Figure 1.2. The main purpose in developing the prioritisation scheme for DH was to develop a dedicated priority setting method capable of identifying chemicals in air, water, soil and foodstuffs that might pose a significant risk to human health following low level environmental exposure. The methodology was developed in order to identify compounds that required further assessment and those that had data gaps. More detailed risk assessments were conducted at a later stage on those compounds prioritised as being of high importancea. The screening methodology was developed for ‘existing chemicals’ as these are of greatest concern because data on their toxicity and/or fate and behaviour are often unknownb. The production of a priority list was designed to highlight compounds that required further regulatory measures to reduce exposure of the general population and for which an in-depth risk characterisation would be necessary to assist in the evaluation and implementation of activities for reducing environmental risks. This might include an assessment of the costs of such risks to human health and the costs of reduction measures. As the scheme also aimed to identify data gaps that might warrant further investigation, the application of default categories for chemicals with no data was also considered. The overall aim was to develop a screening methodology that is quick, clear and simple to use and that can easily be revised to take into account new information on compounds as and when it becomes available. a Benzene (IEH Report on Benzene in the Environment, R12); 4,6-dichlorocresol, hexachloro-1,3-butadiene, tetrachlorobenzene, 2,4,6-trichlorophenol (reports to DH; available from MRC Institute for Environment and Health b ‘Existing Substances’ are those that were placed in the European Union (EU) market before 1981. Prior to 1981 regulatory requirements were related to products intended for certain uses (e.g. veterinary medicines) and did not require assessment of the hazardous properties of any substance before they were released into the market. For substances placed on the market after 1981 (classified as ‘New Substances’) there is a legal requirement to conduct such assessments. Regulatory agencies require the collection of extensive documentation for safety before a chemical, for example, can be used in foods or commercial products. IEH Web Report W14, posted March 2004 at http://www.le.ac.uk/ieh/ 4 This report describes how physicochemical properties and toxicological data were incorporated into a screening model to assess the potential fate and transfer of chemicals between different environmental compartments and to predict the potential human exposure to toxic chemicals through the inhalation of contaminated air and the ingestion of water and food. It must be stressed, however, that the method devised is a simple screening process and that a more detailed assessment is necessary to determine the potential transfer through the foodchain of a chemical and the full extent of any adverse health effects. Sections 2 and 4 present the physicochemical properties, toxicological data and algorithms used to screen the compounds. Section 3 summarises the groups of chemicals that were included in the screening process. The results of the prioritisation scheme and comments on their limitations and constraints are presented in Section 5

Health Hazard Manual for Firefighters

[Excerpt] Firefighters, as well as victims, can be exposed to a variety of toxic substances during a fire. Some of these toxicants are particularly insidious because they are produced by thermal decomposition before smoke makes a fire evident

Assessing the use of NMR chemical shifts for prediction of VLE in non-ideal binary liquid mixtures

A method of estimating vapour liquid equilibrium (VLE) using NMR chemical shift data has been proposed by Xu et al. (2012). This method is based on the concept that the average local composition around each species is determined by the thermodynamics of the system, and also determines the screening of the NMR active groups within that molecule, and so their NMR chemical shifts. Xu et al.‘s method has been replicated and verified; results are confirmed to be accurate for alcohol + hydrocarbon mixtures, giving VLE predictions of comparable accuracy to the UNIFAC, generally considered the best predictive activity coefficient model available. However, for more strongly non-ideal mixtures, the method becomes less reliable, giving significantly less accurate predictions of total pressure than UNIFAC. Several causes for this are identified. The model proposed by Xu et al. (2012) is unable to fit minima or maxima in chemical shifts, which are observed experimentally in some binary mixtures. Different NMR resonances within the same molecule lead to different predictions of VLE, clearly an un-physical result. The thermodynamics of strongly non-ideal mixtures are determined by more complex interactions than a simple description of average local composition around each component in the mixtures, for example strong and directional hydrogen bonds. Different groups within the same molecule may have different local compositions in their immediate vicinity; for example in the case of alcohol + water mixtures, one would expect a clustering of water molecules around the hydroxyl group but not the aliphatic group. Hence, the concept of a simple local composition model is not valid for these more complex cases, and it is therefore not surprising that a model based on this simple concept is often not effective in predicting VLE.C. D’Agostino would like to acknowledge Wolfson College, Cambridge, for supporting his research activities.This is the accepted manuscript. The final version is available from Elsevier at http://www.sciencedirect.com/science/article/pii/S0009250914004461