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Fluorine Chemistry 2016
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Fluorine Chemistry 2016

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 August 2016) | Viewed by 114118

Special Issue Editor

Prof. Dr. Bela Torok

E-Mail Website
Guest Editor
Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Blvd., Boston, MA 02125, USA
Interests: organofluorine chemistry; heterogeneous catalysis; heterocyclic chemistry; asymmetric synthesis; catalytic hydrogenation; microwave-assisted organic synthesis; medicinal chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Since the discovery of the beneficial effects of fluorine incorporation into organic molecules the synthesis and application of organofluorine compounds underwent an explosion like development. The major driving force of such developments was the pharmaceutical industry; however, organofluorine compounds are widely applied in many other applications from plastics, to refrigeration.
In this special issue, our goal is to provide an overview of this exciting research field, as broad as possible, highlighting recent developments in the design, synthesis and application of fluorine compounds.
It is our hope that this Special Issue on Fluorine Chemistry will become an attractive forum to scientists who either work on the synthesis of fluorinated compounds, or apply these compounds for different purposes. Thus this issue will be an excellent medium to present synthesis, structural analysis, pharmacological and therapeutic potential and other applications of fluorine compounds. I strongly encourage authors to submit papers for this Special Issue on Fluorine Chemistry, within the scope of Molecules. I hope that the topics covered will reflect the vast array of synthetic and application possibilities and generate potential future developments in this and related fields.

Dr. Bela Torok
Guest Editor

Manuscript Submission Information

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Keywords

  • fluorine
  • synthesis
  • medicinal chemistry
  • pharmacology
  • polymer
  • imaging
  • probe molecules
  • environmental
  • structural analysis
  • nanoparticles

Published Papers (17 papers)

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Research

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14364 KiB  
Article
Plasma Processing with Fluorine Chemistry for Modification of Surfaces Wettability
by Veronica Satulu, Maria Daniela Ionita, Sorin Vizireanu, Bogdana Mitu and Gheorghe Dinescu
Molecules 2016, 21(12), 1711; https://doi.org/10.3390/molecules21121711 - 13 Dec 2016
Cited by 23 | Viewed by 6071
Abstract
Using plasma in conjunction with fluorinated compounds is widely encountered in material processing. We discuss several plasma techniques for surface fluorination: deposition of fluorocarbon thin films either by magnetron sputtering of polytetrafluoroethylene targets, or by plasma-assisted chemical vapor deposition using tetrafluoroethane as a [...] Read more.
Using plasma in conjunction with fluorinated compounds is widely encountered in material processing. We discuss several plasma techniques for surface fluorination: deposition of fluorocarbon thin films either by magnetron sputtering of polytetrafluoroethylene targets, or by plasma-assisted chemical vapor deposition using tetrafluoroethane as a precursor, and modification of carbon nanowalls by plasma treatment in a sulphur hexafluoride environment. We showed that conformal fluorinated thin films can be obtained and, according to the initial surface properties, superhydrophobic surfaces can be achieved. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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1093 KiB  
Article
A Stereocontrolled Protocol to Highly Functionalized Fluorinated Scaffolds through a Fluoride Opening of Oxiranes
by Attila Márió Remete, Melinda Nonn, Santos Fustero, Ferenc Fülöp and Loránd Kiss
Molecules 2016, 21(11), 1493; https://doi.org/10.3390/molecules21111493 - 17 Nov 2016
Cited by 12 | Viewed by 4790
Abstract
A novel selective and substrate-dependent synthetic protocol has been developed towards the synthesis of various fluorine-containing, highly functionalized cycloalkane derivatives. The method involves the stereoselective epoxidation of some unsaturated cyclic β-amino acid derivatives as model compounds, followed by a regioselective fluoride opening of [...] Read more.
A novel selective and substrate-dependent synthetic protocol has been developed towards the synthesis of various fluorine-containing, highly functionalized cycloalkane derivatives. The method involves the stereoselective epoxidation of some unsaturated cyclic β-amino acid derivatives as model compounds, followed by a regioselective fluoride opening of oxiranes under various conditions with Deoxofluor and XtalFluor-E reagents, thereby offering an insight into this new epoxide opening methodology with fluoride. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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5455 KiB  
Article
Comparative Studies of Interactions between Fluorodihydroquinazolin Derivatives and Human Serum Albumin with Fluorescence Spectroscopy
by Yi Wang, Meiqing Zhu, Feng Liu, Xiangwei Wu, Dandan Pan, Jia Liu, Shisuo Fan, Zhen Wang, Jun Tang, Risong Na, Qing X. Li, Rimao Hua and Shangzhong Liu
Molecules 2016, 21(10), 1373; https://doi.org/10.3390/molecules21101373 - 14 Oct 2016
Cited by 17 | Viewed by 4932
Abstract
In the present study, 3-(fluorobenzylideneamino)-6-chloro-1-(3,3-dimethylbutanoyl)-phenyl-2,3-dihydroquinazolin-4(1H)-one (FDQL) derivatives have been designed and synthesized to study the interaction between fluorine substituted dihydroquinazoline derivatives with human serum albumin (HSA) using fluorescence, circular dichroism and Fourier transform infrared spectroscopy. The results indicated that the FDQL [...] Read more.
In the present study, 3-(fluorobenzylideneamino)-6-chloro-1-(3,3-dimethylbutanoyl)-phenyl-2,3-dihydroquinazolin-4(1H)-one (FDQL) derivatives have been designed and synthesized to study the interaction between fluorine substituted dihydroquinazoline derivatives with human serum albumin (HSA) using fluorescence, circular dichroism and Fourier transform infrared spectroscopy. The results indicated that the FDQL could bind to HSA, induce conformation and the secondary structure changes of HSA, and quench the intrinsic fluorescence of HSA through a static quenching mechanism. The thermodynamic parameters, ΔH, ΔS, and ΔG, calculated at different temperatures, revealed that the binding was through spontaneous and hydrophobic forces and thus played major roles in the association. Based on the number of binding sites, it was considered that one molecule of FDQL could bind to a single site of HSA. Site marker competition experiments indicated that the reactive site of HSA to FDQL mainly located in site II (subdomain IIIA). The substitution by fluorine in the benzene ring could increase the interactions between FDQL and HSA to some extent in the proper temperature range through hydrophobic effect, and the substitution at meta-position enhanced the affinity greater than that at para- and ortho-positions. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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10300 KiB  
Article
Effects of (Oxy-)Fluorination on Various High-Performance Yarns
by Iris Kruppke, Matthias Bartusch, Rico Hickmann, Rolf-Dieter Hund and Chokri Cherif
Molecules 2016, 21(9), 1127; https://doi.org/10.3390/molecules21091127 - 26 Aug 2016
Cited by 8 | Viewed by 5423
Abstract
In this work, typical high-performance yarns are oxy-fluorinated, such as carbon fibers, ultra-high-molecular-weight polyethylene, poly(p-phenylene sulfide) and poly(p-phenylene terephthalamide). The focus is on the property changes of the fiber surface, especially the wetting behavior, structure and chemical composition. Therefore, [...] Read more.
In this work, typical high-performance yarns are oxy-fluorinated, such as carbon fibers, ultra-high-molecular-weight polyethylene, poly(p-phenylene sulfide) and poly(p-phenylene terephthalamide). The focus is on the property changes of the fiber surface, especially the wetting behavior, structure and chemical composition. Therefore, contact angle, XPS and tensile strength measurements are performed on treated and untreated fibers, while SEM is utilized to evaluate the surface structure. Different results for the fiber materials are observed. While polyethylene exhibits a relevant impact on both surface and bulk properties, polyphenylene terephthalamide and polyphenylene sulfide are only affected slightly by (oxy-)fluorination. The wetting of carbon fiber needs higher treatment intensities, but in contrast to the organic fibers, even its textile-physical properties are enhanced by the treatment. Based on these findings, the capability of (oxy-)fluorination to improve the adhesion of textiles in fiber-reinforced composite materials can be derived. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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2895 KiB  
Article
Fluorinated Polyurethanes, Synthesis and Properties
by Olga Smirnova, Alexey Glazkov, Alexander Yarosh and Alexey Sakharov
Molecules 2016, 21(7), 904; https://doi.org/10.3390/molecules21070904 - 12 Jul 2016
Cited by 14 | Viewed by 6070
Abstract
Fluorinated polyurethanes with a glass transition temperature as low as −139 °C and a decomposition onset temperature of 247–330 °C were prepared by a reaction of fluorinated alcohols with aromatic and cycloaliphatic diisocyanates in solution or melt. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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398 KiB  
Article
Synthesis of Regiospecifically Fluorinated Conjugated Dienamides
by Mohammad Chowdhury, Samir K. Mandal, Shaibal Banerjee and Barbara Zajc
Molecules 2014, 19(4), 4418-4432; https://doi.org/10.3390/molecules19044418 - 10 Apr 2014
Cited by 11 | Viewed by 5959
Abstract
Modular synthesis of regiospecifically fluorinated 2,4-diene Weinreb amides, with defined stereochemistry at both double bonds, was achieved via two sequential Julia-Kocienski olefinations. In the first step, a Z-a-fluorovinyl Weinreb amide unit with a benzothiazolylsulfanyl substituent at the allylic position was assembled. This [...] Read more.
Modular synthesis of regiospecifically fluorinated 2,4-diene Weinreb amides, with defined stereochemistry at both double bonds, was achieved via two sequential Julia-Kocienski olefinations. In the first step, a Z-a-fluorovinyl Weinreb amide unit with a benzothiazolylsulfanyl substituent at the allylic position was assembled. This was achieved via condensation of two primary building blocks, namely 2-(benzo[d]thiazol-2-ylsulfonyl)-2-fluoro-N-methoxy-N-methylacetamide (a Julia-Kocienski olefination reagent) and 2-(benzo[d]thiazol-2-ylthio)acetaldehyde (a bifunctional building block). This condensation was highly Z-selective and proceeded in a good 76% yield. Oxidation of benzothiazolylsulfanyl moiety furnished a second-generation Julia-Kocienski olefination reagent, which was used for the introduction of the second olefinic linkage via DBU-mediated condensations with aldehydes, to give (2Z,4E/Z)-dienamides in 50%–74% yield. Although olefinations were 4Z-selective, (2Z,4E/Z)-2-fluoro-2,4-dienamides could be readily isomerized to the corresponding 5-substituted (2Z,4E)-2-fluoro-N-methoxy-N-methylpenta-2,4-dienamides in the presence of catalytic iodine. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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237 KiB  
Article
Pauson-Khand Reaction of Internal Dissymmetric Trifluoromethyl Alkynes. Influence of the Alkene on the Regioselectivity
by Nuria Aiguabella, Elsa M. Arce, Carlos Del Pozo, Xavier Verdaguer and Antoni Riera
Molecules 2014, 19(2), 1763-1774; https://doi.org/10.3390/molecules19021763 - 03 Feb 2014
Cited by 8 | Viewed by 6457
Abstract
The scope of the Pauson-Khand reaction (PKR) of internal trifluoromethyl alkynes, previously described with norbornadiene, is expanded to norbornene and ethylene. A thorough structural analysis of the resulting PK adducts has been carried out to unveil that α-trifluoromethylcyclopentenones are preferred in all cases, [...] Read more.
The scope of the Pauson-Khand reaction (PKR) of internal trifluoromethyl alkynes, previously described with norbornadiene, is expanded to norbornene and ethylene. A thorough structural analysis of the resulting PK adducts has been carried out to unveil that α-trifluoromethylcyclopentenones are preferred in all cases, independently of the electronic properties of the alkyne. The regioselectivity observed with norbornadiene and ethylene is higher than in the case of norbornene. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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776 KiB  
Article
Crystal Structures and Antifungal Activities of Fluorine-Containing Thioureido Complexes with Nickel(II)
by Chun Li, Wen Yang, Huanhuan Liu, Mengying Li, Weiqun Zhou and Juan Xie
Molecules 2013, 18(12), 15737-15749; https://doi.org/10.3390/molecules181215737 - 17 Dec 2013
Cited by 10 | Viewed by 5314
Abstract
Ni(II) complexes with N-2-fluorobenzoylpiperidine-1-carbothioimidate (L2−), N-4-fluorobenzoylpiperidine-1-carbothioimidate (L3−), N-2-fluorobenzoylmorpholine- 1-carbothioimidate (L5−) and N-4-fluorobenzoylmorpholine-1-carbothioimidate (L6−) have been synthesized and characterized by elemental analysis, FTIR and 1H-NMR. The crystal structures of three ligands (HL2, HL3 [...] Read more.
Ni(II) complexes with N-2-fluorobenzoylpiperidine-1-carbothioimidate (L2−), N-4-fluorobenzoylpiperidine-1-carbothioimidate (L3−), N-2-fluorobenzoylmorpholine- 1-carbothioimidate (L5−) and N-4-fluorobenzoylmorpholine-1-carbothioimidate (L6−) have been synthesized and characterized by elemental analysis, FTIR and 1H-NMR. The crystal structures of three ligands (HL2, HL3 and HL6) and the corresponding Ni(II) complexes ([Ni(L2)2], [Ni(L3)2] and [Ni(L6)2]) have been determined by X-ray diffraction. The antifungal activities of the Ni(II) complexes together and the corresponding ligands against the fungi Botrytis cinerea, Trichoderma spp., Myrothecium and Verticillium spp. have been investigated. The experimental results showed that the ligands and their complexes have antifungal abilities. When the fluorine was substituted on the para-benzoyl moiety, the antifungal activity of the ligands was obviously increased. Moreover, the ligands were stronger than their complexes in inhibiting fungal activities. The antifungal ability of HL6 is especially strong, and similar to that of the commercial fungicide fluconazole. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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300 KiB  
Article
Synthesis of δ-Oxo-1,1-bis(triflyl)alkanes and Their Acidities
by Hikaru Yanai, Masaya Fujita, Arata Takahashi, Min Zhang, Masaaki Mishima, Akira Kotani, Takashi Matsumoto and Takeo Taguchi
Molecules 2013, 18(12), 15531-15540; https://doi.org/10.3390/molecules181215531 - 13 Dec 2013
Cited by 7 | Viewed by 5309
Abstract
The reaction of 1,1-bis(triflyl)ethylene generated in situ with enolizable carbonyls yielded δ-oxo-1,1-bis(triflyl)alkane derivatives. Their acidities in both the gas and solution phases were determined. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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1621 KiB  
Article
Automated Solid-Phase Radiofluorination Using Polymer-Supported Phosphazenes
by Bente Mathiessen and Fedor Zhuravlev
Molecules 2013, 18(9), 10531-10547; https://doi.org/10.3390/molecules180910531 - 30 Aug 2013
Cited by 11 | Viewed by 5972
Abstract
The polymer supported phosphazene bases PS-P2tBu and the novel PS-P2PEG allowed for efficient extraction of [18F]F− from proton irradiated [18O]H2O and subsequent radiofluorination of a broad range of substrates directly [...] Read more.
The polymer supported phosphazene bases PS-P2tBu and the novel PS-P2PEG allowed for efficient extraction of [18F]F− from proton irradiated [18O]H2O and subsequent radiofluorination of a broad range of substrates directly on the resin. The highest radiochemical yields were obtained with aliphatic sulfonates (69%) and bromides (42%); the total radiosynthesis time was 35–45 min. The multivariate analysis showed that the radiochemical yields and purities were controlled by the resin load, reaction temperature, and column packing effects. The resins could be reused several times with the same or different substrates. The fully automated on-column radiofluorination methodology was applied to the radiosynthesis of the important PET radiotracers [18F]FLT and [18F]FDG. The latter was produced with 40% yield on a 120 GBq scale and passed GMP-regulated quality control required for commercial production of [18F]FDG. The combination of compact form factor, simplicity of [18F]F− recovery and processing, and column reusability can make solid phase radiofluorination an attractive radiochemistry platform for the emerging dose-on-demand instruments for bedside production of PET radiotracers. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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706 KiB  
Article
Design and Synthesis of New N-(5-Trifluoromethyl)-1H-1,2,4-triazol-3-yl Benzenesulfonamides as Possible Antimalarial Prototypes
by Nubia Boechat, Luiz C.S. Pinheiro, Osvaldo A. Santos-Filho and Isabor C. Silva
Molecules 2011, 16(9), 8083-8097; https://doi.org/10.3390/molecules16098083 - 20 Sep 2011
Cited by 52 | Viewed by 9359
Abstract
A rational approach was used to synthesize a new set of 15 1H-1,2,4-triazol-3-yl benzenesulfonamide derivatives with the aim of developing new antimalarial lead compounds. These derivatives were prepared in yields between 50% and 62%, and their structures were elucidated using IR, [...] Read more.
A rational approach was used to synthesize a new set of 15 1H-1,2,4-triazol-3-yl benzenesulfonamide derivatives with the aim of developing new antimalarial lead compounds. These derivatives were prepared in yields between 50% and 62%, and their structures were elucidated using IR, 1H-, 13C-, 19F-NMR, MS and elemental analysis. A docking study based on sulfonamides previously used against malaria identified trifluoromethyl-substituted derivatives to be the best lead compounds for new antimalarial drug development. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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402 KiB  
Communication
Synthesis of No-Carrier-Added 4-[18F]Fluorophenol from 4-Benzyloxyphenyl-(2-thienyl)iodonium Bromide
by Tobias L. Ross, Johannes Ermert and Heinz H. Coenen
Molecules 2011, 16(9), 7621-7626; https://doi.org/10.3390/molecules16097621 - 06 Sep 2011
Cited by 15 | Viewed by 5034
Abstract
4-[18F]Fluorophenol is a versatile synthon for the synthesis of more complex radiopharmaceuticals bearing a 4-[18F]fluorophenoxy moiety. In order to prepare 4-[18F]fluorophenol in no-carrier-added (n.c.a.) form only a nucleophilic labelling method starting from [18F]fluoride is suitable. [...] Read more.
4-[18F]Fluorophenol is a versatile synthon for the synthesis of more complex radiopharmaceuticals bearing a 4-[18F]fluorophenoxy moiety. In order to prepare 4-[18F]fluorophenol in no-carrier-added (n.c.a.) form only a nucleophilic labelling method starting from [18F]fluoride is suitable. In this paper a new, two step radiosynthesis starting from 4-benzyloxyphenyl-(2-thienyl)iodonium bromide and [18F]fluoride with subsequent deprotection is described, yielding n.c.a. [18F]fluorophenol in 34 to 36% radiochemical yield. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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616 KiB  
Article
t-Bu2SiF-Derivatized D2-Receptor Ligands: The First SiFA-Containing Small Molecule Radiotracers for Target-Specific PET-Imaging
by Ljuba Iovkova-Berends, Carmen Wängler, Thomas Zöller, Georg Höfner, Klaus Theodor Wanner, Christian Rensch, Peter Bartenstein, Alexey Kostikov, Ralf Schirrmacher, Klaus Jurkschat and Björn Wängler
Molecules 2011, 16(9), 7458-7479; https://doi.org/10.3390/molecules16097458 - 02 Sep 2011
Cited by 17 | Viewed by 8715
Abstract
The synthesis, radiolabeling and in vitro evaluation of new silicon-fluoride acceptor (SiFA) derivatized D2-receptor ligands is reported. The SiFA-technology simplifies the introduction of fluorine-18 into target specific biomolecules for Positron-Emission-Tomography (PET). However, one of the remaining challenges, especially for small molecules [...] Read more.
The synthesis, radiolabeling and in vitro evaluation of new silicon-fluoride acceptor (SiFA) derivatized D2-receptor ligands is reported. The SiFA-technology simplifies the introduction of fluorine-18 into target specific biomolecules for Positron-Emission-Tomography (PET). However, one of the remaining challenges, especially for small molecules such as receptor-ligands, is the bulkiness of the SiFA-moiety. We therefore synthesized four Fallypride SiFA-conjugates derivatized either directly at the benzoic acid ring system (SiFA-DMFP, SiFA-FP, SiFA-DDMFP) or at the butyl-side chain (SiFA-M-FP) and tested their receptor affinities. We found D2-receptor affinities for all compounds in the nanomolar range (Ki(SiFA-DMFP) = 13.6 nM, Ki(SiFA-FP) = 33.0 nM, Ki(SiFA-DDMFP) = 62.7 nM and Ki(SiFA-M-FP) = 4.21 nM). The radiofluorination showed highest yields when 10 nmol of the precursors were reacted with [18F]fluoride/TBAHCO3 in acetonitrile. After a reversed phased cartridge purification the desired products could be isolated as an injectable solution after only 10 min synthesis time with radiochemical yields (RCY) of more than 40% in the case of SiFA-DMFP resulting in specific activities >41 GBq/µmol (>1,100 Ci/mmol). Furthermore, the radiolabeled products were shown to be stable in the injectable solutions, as well as in human plasma, for at least 90 min. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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932 KiB  
Article
Perfluoro Allyl Fluorosulfate (FAFS): A Versatile Building Block for New Fluoroallylic Compounds
by Ivan Wlassics, Vito Tortelli, Serena Carella, Cristiano Monzani and Giuseppe Marchionni
Molecules 2011, 16(8), 6512-6540; https://doi.org/10.3390/molecules16086512 - 04 Aug 2011
Cited by 12 | Viewed by 7889
Abstract
In this study we will present and discuss both the synthesis of CF2=CFCF2OSO2F (perfluoroallyl fluorosulfate, FAFS), focusing in particular on the important role of C3F6/SO3 ratio, reaction temperature and boron catalyst/SO3 [...] Read more.
In this study we will present and discuss both the synthesis of CF2=CFCF2OSO2F (perfluoroallyl fluorosulfate, FAFS), focusing in particular on the important role of C3F6/SO3 ratio, reaction temperature and boron catalyst/SO3 ratio on FAFS’ yield and selectivity, as well as a wide variety of ionic and radical reactions possible with FAFS. We focused our attention on reactions of FAFS with aliphatic and aromatic alcohols, acyl halides, halides, H2O2, ketones and radicals whose synthesis and reaction mechanisms will be presented and discussed. Particular attention will be devoted to the novel diallyl-fluoroalkyl peroxide obtained. Factors such as pKa and Lowry and Pearson’s Hard/Soft Acid-Base Theory which determine the selectivity between Addition/Elimination vs. Nucleophilic Substitution reaction mechanisms on FAFS will also be presented and discussed. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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258 KiB  
Article
Dehydration of (Perfluoroalkyl)tetramethylcyclopentenols
by Jan Čermák, Thu Huong Nguyen Thi, Jaroslav Včelák and Alena Krupková
Molecules 2011, 16(5), 4031-4044; https://doi.org/10.3390/molecules16054031 - 17 May 2011
Cited by 2 | Viewed by 5272
Abstract
(Perfluoroalkyl) tetramethylcyclopentenols (alkyl = n-butyl, n-hexyl, n-octyl) were dehydrated to a complex mixture of endo, endo-(perfluoroalkyl) tetramethyl-cyclopentadienes and their endo-, exo-isomers. It was found in preliminary screening experiments that the best reagent for this transformation, giving an 89% [...] Read more.
(Perfluoroalkyl) tetramethylcyclopentenols (alkyl = n-butyl, n-hexyl, n-octyl) were dehydrated to a complex mixture of endo, endo-(perfluoroalkyl) tetramethyl-cyclopentadienes and their endo-, exo-isomers. It was found in preliminary screening experiments that the best reagent for this transformation, giving an 89% yield of isomeric product mixture, was P2O5 in benzene at 80-90 °C. Products were characterized on the basis of their mass spectra and retention time information, and some peaks in the mass spectra were identified from their molecular fragments. Structures were assigned to the three most abundant products of (perfluorohexyl)tetramethylcyclopentenol dehydration. Formal dehydration kinetics showed a second order reaction in benzene but zeroth order with induction period in chlorobenzene, suggesting mass transfer limitations in the more polar chlorobenzene. Some of the products were formed by consecutive isomerization of the others, as shown by the kinetic analysis. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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250 KiB  
Article
General Pathway for a Convenient One-Pot Synthesis of Trifluoromethyl-Containing 2-amino-7-alkyl(aryl/heteroaryl)-1,8-naphthyridines and Fused Cycloalkane Analogues
by Helio G. Bonacorso, Rosália Andrighetto, Nícolas Krüger, Nilo Zanatta and Marcos A. P. Martins
Molecules 2011, 16(4), 2817-2832; https://doi.org/10.3390/molecules16042817 - 30 Mar 2011
Cited by 13 | Viewed by 9514
Abstract
A convenient and general method for the synthesis in 26–73% yields of a new series of 7-alkyl(aryl/heteroaryl)-2-amino-5-trifluoromethyl-1,8-naphthyridines from direct cyclocondensation reactions of 4-alkoxy-1,1,1-trifluoroalk-3-en-2-ones [CF3C(O)CH=C(R1)OR, where R1 = H, Me, Ph, 4-MePh, 4-OMePh, 4-FPh, 4-BrPh, 4-NO2Ph, 2-furyl, [...] Read more.
A convenient and general method for the synthesis in 26–73% yields of a new series of 7-alkyl(aryl/heteroaryl)-2-amino-5-trifluoromethyl-1,8-naphthyridines from direct cyclocondensation reactions of 4-alkoxy-1,1,1-trifluoroalk-3-en-2-ones [CF3C(O)CH=C(R1)OR, where R1 = H, Me, Ph, 4-MePh, 4-OMePh, 4-FPh, 4-BrPh, 4-NO2Ph, 2-furyl, 2-thienyl and R = Me, Et] with 2,6-diaminopyridine (2,6-DAP), under mild conditions, is described. Another synthetic route also allowed the synthesis of 2-amino-5-trifluoromethyl-cycloalka[b][1,8]naphthyridines in 33–36% yields, from direct or indirect cyclo-condensation reactions of five-, six- and seven-membered 2-trifluoroacetyl-1-methoxy-cycloalkenes with 2,6-DAP. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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Review

Jump to: Research

1157 KiB  
Review
Recent Advances in the Application of SelectfluorTMF-TEDA-BF4 as a Versatile Mediator or Catalyst in Organic Synthesis
by Stojan Stavber
Molecules 2011, 16(8), 6432-6464; https://doi.org/10.3390/molecules16086432 - 29 Jul 2011
Cited by 80 | Viewed by 11166
Abstract
SelectfluorTM F-TEDA-BF4 (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2]octane bis(tetrafluoroborate) is not only one of the most efficient and popular reagents for electrophilic fluorination, but as a strong oxidant is also a convenient mediator or catalyst of several “fluorine-free” functionalizations of organic compounds. Its applications as [...] Read more.
SelectfluorTM F-TEDA-BF4 (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2]octane bis(tetrafluoroborate) is not only one of the most efficient and popular reagents for electrophilic fluorination, but as a strong oxidant is also a convenient mediator or catalyst of several “fluorine-free” functionalizations of organic compounds. Its applications as a mediator in transformations of oxidizable functional groups or gold-catalyzed C-C and C-heteroatom oxidative coupling reactions, a catalyst in formation of various heterocyclic rings, a reagent or catalyst of various functionalizations of electron-rich organic compounds (iodination, bromination, chlorination, nitration, thiocyanation, sulfenylation, alkylation, alkoxylation), a catalyst of one-pot-multi-component coupling reactions, a catalyst of regioselective ring opening of epoxides, a deprotection reagent for various protecting groups, and a mediator for stereoselective rearrangement processes of bicyclic compounds are reviewed and discussed. Full article
(This article belongs to the Special Issue Fluorine Chemistry 2016)
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