1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• illustrated the way of utilizing different types of noncovalent interactions including hydrogen bonding, halogen and chalcogen bonding for the selective detection of anions by triazolium macrocycles. The selectivity and the ability of detection of anions are highly dependent on the solvent polarity. We have

A golden opportunity: benzofuranone modifications of aurones and their influence on optical properties, toxicity, and potential as dyes

• Joza Schmitt and
• Scott T. Handy

Beilstein J. Org. Chem. 2019, 15, 1781–1785, doi:10.3762/bjoc.15.171

• at the 5-position resulted in a shift to longer wavelength by roughly 20 nm compared to a methoxy substituent at the 4-position and a strong dependence upon solvent polarity. While this shift was quite reasonably attributed to the inductive effect of the oxygen, no other substitution was studied

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D–π–)₂A fluorescent dyes

• Keiichi Imato,
• Toshiaki Enoki,
• Koji Uenaka and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2019, 15, 1712–1721, doi:10.3762/bjoc.15.167

• characteristic band of the (D–π–)2A fluorescent dyes show bathochromic shifts in the order of OUY-2 < OUK-2 < OUJ-2. Moreover, the photoabsorption bands of the (D–π–)2A fluorescent dyes are nearly independent of solvent polarity, while the fluorescence bands showed bathochromic shifts with increasing solvent

• < OUJ-2, which is in agreement with the increase in the electron-withdrawing ability of the azine ring in the order of pyridyl group < pyrazyl group < triazyl group. The photoabsorption spectra of the three dyes are nearly independent of solvent polarity. This indicates that the electronic and

• structural characteristics of both the ground and Franck–Condon (FC) excited states do not differ much with a change in solvent polarity. The molar extinction coefficient (εmax) for the ICT band is ca. 100000 M−1 cm−1 for OUY-2, 75000 M−1 cm−1 for OUK-2 and 80000 M−1 cm−1 for OUJ-2. The corresponding

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• , respectively, by plotting the maximum emission wavenumbers of 2,6-TNS/1,8-ANS in a set of solvents as a function of solvent polarity ET(30) (Figure 1e and 1f). ET(30) values for the involved solvents (water, methanol, ethanol, propanol, butanol, glycerol and ethylene glycol) and the maximum emission

• point on the titration curve indicates a 1:1 binding stoichiometry between GC5A and P-TPE. Ka was fitted according to a 1:1 binding model giving a value of (8.4 ± 1.1) × 107 M−1 (Figure 2b, Table 1). The emission wavelengths of classical AIEgens are scarcely affected by solvent polarity, which is a

Strong hyperconjugative interactions limit solvent and substituent influence on conformational equilibrium: the case of cis-2-halocyclohexylamines

• Camila B. Francisco,
• Cleverton S. Fernandes,
• Ulisses Z. de Melo,
• Roberto Rittner,
• Gisele F. Gauze and
• Ernani A. Basso

Beilstein J. Org. Chem. 2019, 15, 818–829, doi:10.3762/bjoc.15.79

• methanol-d4. The conformational preference was affected neither by the solvent polarity nor the halogen size, suggesting the presence of strong stereoelectronic effects being responsible for the conformational behavior in these systems. Theoretical calculations are in agreement with experimental data, the

Conformational signature of Ishikawa´s reagent using NMR information from diastereotopic fluorines

• Laize A. F. Andrade,
• Lucas A. Zeoly,
• Rodrigo A. Cormanich and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2019, 15, 506–512, doi:10.3762/bjoc.15.44

• dipole moments and, consequently, the conformer populations are expected to change with the solvent polarity [29]. Indeed, the 1H NMR outcomes in C6D12 (dielectric constant ε = 2.2), CDCl3 (ε = 4.8) and C5D5N (ε = 12.4) solutions are informative on the rotation of H–C2–C1–F and conformational equilibrium

• 1C is not expected when the solvent varies, because of their similar molecular dipole moments. In turn, the populations of conformer 1A are not prone to increase by increasing the solvent polarity, because of their smaller molecular dipole moments compared to 1B and 1C. So, the observed changes in

• Ishikawa´s reagent. In addition, this equilibrium shifts from 1Ab to 1Cc when increasing the solvent polarity. These findings are in complete agreement with the conformational energy data provided in Table 2, which were obtained from high level DFT calculations (1Cb is not a minimum-energy conformer). The

Synthesis and fluorescent properties of N(9)-alkylated 2-amino-6-triazolylpurines and 7-deazapurines

• Andrejs Šišuļins,
• Jonas Bucevičius,
• Yu-Ting Tseng,
• Irina Novosjolova,
• Kaspars Traskovskis,
• Ērika Bizdēna,
• Huan-Tsung Chang,
• Sigitas Tumkevičius and
• Māris Turks

Beilstein J. Org. Chem. 2019, 15, 474–489, doi:10.3762/bjoc.15.41

• increases with the increase of solvent polarity. Additionally, X-ray analysis of 2,6-diazidopurine 2'-deoxyribonucleoside revealed the exclusive existence of the azido tautomer in the solid state [41]. The discovered ability of the azido group to be substituted with amines at C(2) position was used for the

• showed pronounced changes with solvent polarity in terms of emission maxima and quantum yields, though the absorption spectra showed minor or no changes with increasing solvent polarity indicating small dipole moment in the ground state. A good linear correlation between the fluorescence QY and the

• same solvents (Table 4). Non-linear dependency in increase of emission maxima is observed (Table 4) with increasing polarity parameter (ET(30)), thus indicating that the sensitivity to solvent polarity is not the only major solute–solvent interaction and the emission maxima are also influenced by other

Learning from B₁₂ enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

• Keishiro Tahara,
• Ling Pan,
• Toshikazu Ono and
• Yoshio Hisaeda

Beilstein J. Org. Chem. 2018, 14, 2553–2567, doi:10.3762/bjoc.14.232

• liquid layer could be recycled for further reactions. More interestingly, the catalytic ability of 1 increased nearly four times the reaction using DMF as solvent. This was consistent with the Hughes–Ingold prediction of solvent polarity effects on reaction rates [111]. We also developed a visible-light

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

• Cristina Cebrián and
• Matteo Mauro

Beilstein J. Org. Chem. 2018, 14, 1459–1481, doi:10.3762/bjoc.14.124

• properties. Indeed, bathochromic shifts in the emission energy were observed upon either grinding or incrementing solvent polarity. This emission was attributed to a radiative transition with triplet metal–metal-to-ligand charge transfer character (3MMLCT), which ultimately strongly depends on the platinum

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• , for the cycloaddition of the structurally similar ethyl phenylpropiolate in various solvents only a small decrease of the bimolecular rate constant with increasing solvent polarity (in terms of relative permittivity) was observed excluding a transition state having a polarized character. Finally

• , substitution effects in the 3-(4-substituted phenyl) group of sydnones were studied and a relatively low Hammett reaction constant ρ ≈ +0.8 was estimated from four derivatives (MeO, Me, H and Cl). An even smaller dependence of the rate constants on the solvent polarity and substituent effect sensitivity (ρ

Regioselective decarboxylative addition of malonic acid and its mono(thio)esters to 4-trifluoromethylpyrimidin-2(1H)-ones

• Sergii V. Melnykov,
• Andrii S. Pataman,
• Yurii V. Dmytriv,
• Svitlana V. Shishkina,
• Mykhailo V. Vovk and
• Volodymyr A. Sukach

Beilstein J. Org. Chem. 2017, 13, 2617–2625, doi:10.3762/bjoc.13.259

• , unique heterocyclic ketimines, react with malonic acid under organic base catalysis to regioselectively provide either Michael- or Mannich-type decarboxylative addition products depending on solvent polarity. Malonic mono(thio)esters give exclusively Michael-type products. The two regioisomeric products

• supported by the known effect of solvent polarity on the decarboxylation rate of malonic acid derivatives which was claimed to be faster in polar media [40]. To study the substrate scope of the regioselective additions of malonic acid, we introduced substituted pyrimidones 2b–m in the reaction and performed

• . Presumably, in this case, the kinetically controlled Michael-type intermediate C is even far more prone to decarboxylation than the dicarboxylate intermediate A (Table 1) and hence, the reaction is sufficiently regioselective irrespective of the solvent polarity (Table 3, entries 1, and 6–9). Performing the

Synthesis, effect of substituents on the regiochemistry and equilibrium studies of tetrazolo[1,5-a]pyrimidine/2-azidopyrimidines

• Elisandra Scapin,
• Paulo R. S. Salbego,
• Caroline R. Bender,
• Alexandre R. Meyer,
• Anderson B. Pagliari,
• Tainára Orlando,
• Geórgia C. Zimmer,
• Clarissa P. Frizzo,
• Helio G. Bonacorso,
• Nilo Zanatta and
• Marcos A. P. Martins

Beilstein J. Org. Chem. 2017, 13, 2396–2407, doi:10.3762/bjoc.13.237

• influenced by the polarity of the solvent. Upon increasing the solvent polarity, an increase in the amount of the tetrazole form in equilibrium is usually observed [28][36]. In general, the tetrazole form 3a–g is predominant in the mixture at a proportion greater than 4:1 relative to the azide form 4a–g. The

• compared to its stability in CDCl3. A study of the azide–tetrazole equilibrium in several furo[2,3-e][1,5-c]pyrimidines was also performed by Sirakanyan et al. [36]. They showed that upon increasing the solvent polarity of CCl4 (ε 2.3) to DMSO-d6 (ε 46.7), the amount of the tetrazolo form increases (from 6

Curcuminoid–BF₂ complexes: Synthesis, fluorescence and optimization of BF₂ group cleavage

• Henning Weiss,
• Jeannine Reichel,
• Helmar Görls,
• Kilian Rolf Anton Schneider,
• Mathias Micheel,
• Michael Pröhl,
• Michael Gottschaldt,
• Benjamin Dietzek and
• Wolfgang Weigand

Beilstein J. Org. Chem. 2017, 13, 2264–2272, doi:10.3762/bjoc.13.223

• known property for curcumin and its derivatives [32][33], we investigated the solvatochromism of 2b as an example compound in five different solvents (Figure 3). Solvents were chosen by their ET(30) values of polarity as determined by Reichardt [34]. With rising solvent polarity, the vibrational

Conformational impact of structural modifications in 2-fluorocyclohexanone

• Francisco A. Martins,
• Josué M. Silla and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2017, 13, 1781–1787, doi:10.3762/bjoc.13.172

• population of the equatorial conformer increased with the solvent polarity, as dipolar repulsion between Y and F decreases in solvents with increasing dielectric constants. Nuclear magnetic resonance (NMR) parameters, namely chemical shifts and coupling constants, can be useful to provide information on

New electroactive asymmetrical chalcones and therefrom derived 2-amino- / 2-(1H-pyrrol-1-yl)pyrimidines, containing an N-[ω-(4-methoxyphenoxy)alkyl]carbazole fragment: synthesis, optical and electrochemical properties

• Daria G. Selivanova,
• Alexei A. Gorbunov,
• Olga A. Mayorova,
• Alexander N. Vasyanin,
• Igor V. Lunegov,
• Elena V. Shklyaeva and
• Georgii G. Abashev

Beilstein J. Org. Chem. 2017, 13, 1583–1595, doi:10.3762/bjoc.13.158

• ], which exhibit the redshift of a longwave absorption/emission maxima along with the increase of a solvent polarity. Maybe this is a result of a molecule symmetry breaking in its excited state [27]. Taking into account all the factors mentioned above, we have started the investigation of solvatochromic

• neighboring charge or dipole by virtue of nonspecific dielectric interactions [28]. This parameter was determined by Kamlet, Abboud and Taft [29]. The measurement results are displayed in Figure 2. The obtained data demonstrate that the increase of solvent polarity affords the redshift of the longwave UV

• of electronic density of both molecules [32]. The further increase in the solvent polarity leads in both cases to a hypsochromic shift of a long-wave absorption maximum. Absorption and emission spectra of 2-(1H-pyrrol-1-yl)pyrimidines 8a,b are presented in Figure 6. Absorption bands in the 280–450 nm

Interactions between photoacidic 3-hydroxynaphtho[1,2-b]quinolizinium and cucurbit[7]uril: Influence on acidity in the ground and excited state

• Jonas Becher,
• Daria V. Berdnikova,
• Darinka Dzubiel,
• Heiko Ihmels and
• Phil M. Pithan

Beilstein J. Org. Chem. 2017, 13, 203–212, doi:10.3762/bjoc.13.23

• the absorption maximum with increasing solvent polarity (CH3CN: 457 nm, MeOH: 432 nm, H2O: 415 nm). The prototropic equilibrium between 2 and 2cB is significantly shifted to the deprotonated form 2cB in the excited state, as commonly observed for hydroxy-substituted arenes. As a result, the pKa* of 2

Synthesis and fluorosolvatochromism of 3-arylnaphtho[1,2-b]quinolizinium derivatives

• Phil M. Pithan,
• David Decker,
• Manlio Sutero Sardo,
• Giampietro Viola and
• Heiko Ihmels

Beilstein J. Org. Chem. 2016, 12, 854–862, doi:10.3762/bjoc.12.84

• . The resulting cationic biaryl derivatives exhibit pronounced fluorosolvatochromic properties. First photophysical studies in different solvents showed that the emission energy of the biaryl derivatives decreases with increasing solvent polarity. This red-shifted emission in polar solvents is explained

• characteristic of donor–acceptor dyes, namely a cumulative red shift of the emission maximum with increasing solvent polarity, along with a broad, unstructured band structure [1][2]. To assess the effect of the solvent on the emission of compound 6e several different solvents were employed. Unfortunately, many

• –acceptor dyes [3]. However, the linear regression analysis of a plot of the emission energy versus solvent polarity, as quantified by the ET(30) value, did not produce a good correlation, which indicates that solvent properties other than the polarity also contribute to some extent to the stabilization or

Amino-functionalized (meth)acryl polymers by use of a solvent-polarity sensitive protecting group (Br-t-BOC)

• Helmut Ritter,
• Monir Tabatabai and
• Markus Herrmann

Beilstein J. Org. Chem. 2016, 12, 245–252, doi:10.3762/bjoc.12.26

• , IR, GPC and DSC methods. The kinetics of the deprotection step was followed by 1H NMR spectroscopy. The solvent polarity and neighboring group effects on the kinetics of deprotection are discussed. Keywords: amino group protection; bromo-tert-butyloxycarbonyl; deprotection; free radical

• polymerization; (meth)acryl polymers; neighboring group effects; solvent polarity; Introduction Amino groups are important functionalities in polymer chemistry, e.g., for hardening various epoxy resins [1]. However, they easily react in an undesired side reaction with electron-poor double bonds of (meth

• this in mind, the bromo-tert-butyloxycarbonyl (Br-t-BOC) group represents the first known solvent-polarity sensitive amino-protecting group. As shown in Figure 1, this group is stable in nonpolar solvents because of high activation energy and easily decomposes in a more polar environment because of

Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid

• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Anna Gajda,
• Tadeusz Gajda,
• Anna Makal,
• Arnaud Brosseau and
• Rémi Métivier

Beilstein J. Org. Chem. 2015, 11, 2451–2458, doi:10.3762/bjoc.11.266

• practically did not influence the electronic absorption and emission spectra. Structured emission bands were observed showing only a small effect of solvent polarity (Figure 1). However, the fluorescence quantum yields of 3a–d and 4 were significantly higher than that of 5. In order to explain this phenomenon

Why base-catalyzed isomerization of N-propargyl amides yields mostly allenamides rather than ynamides

• Armando Navarro-Vázquez

Beilstein J. Org. Chem. 2015, 11, 1441–1446, doi:10.3762/bjoc.11.156

• ). Nonetheless, the above results suggest that varying the reaction conditions (perhaps solvent polarity) could eventually lead to the observation of the allenimides. NMR deuteration studies could be of help to experimentally eliminate possible kinetic effects in the observed lack of reactivity [19]. Having

Microsolvation and sp²-stereoinversion of monomeric α-(2,6-di-tert-butylphenyl)vinyllithium as measured by NMR

• Rudolf Knorr,
• Monika Knittl and
• Eva C. Rossmann

Beilstein J. Org. Chem. 2014, 10, 2521–2530, doi:10.3762/bjoc.10.263

• place of 47%) THF solution (−8 °C in Table S2, [15]); however, this weak acceleration might also be due to the increased solvent polarity. The pseudomonomolecular, ionic mechanism in Scheme 3 had previously [11] been deduced through finding a Hammett reaction constant of ρ = +5.2 for the sp2

Scalable synthesis of 5,11-diethynylated indeno[1,2-b]fluorene-6,12-diones and exploration of their solid state packing

• Bradley D. Rose,
• Peter J. Santa Maria,
• Aaron G. Fix,
• Chris L. Vonnegut,
• Lev N. Zakharov,
• Sean R. Parkin and
• Michael M. Haley

Beilstein J. Org. Chem. 2014, 10, 2122–2130, doi:10.3762/bjoc.10.219

• different in polar solvents when compared to non-polar solvents, thus leading to an energy shift of this transition. Likewise if the S0→S1 transition was a π→π* there should be essentially no change in the transition energy when changing solvent polarity. We found that the shift in the spectrum upon

• changing solvent polarity in going from n-hexane to acetone was 0.02 eV, supporting our hypothesis that the 450–550 nm absorption is indeed a π→π* transition as indicated by calculations. X-ray crystallography. We explored the solid-state packing geometries resulting from altering the substitution on the

Photo, thermal and chemical degradation of riboflavin

• Muhammad Ali Sheraz,
• Sadia Hafeez Kazi,
• Sofia Ahmed,
• Zubair Anwar and
• Iqbal Ahmad

Beilstein J. Org. Chem. 2014, 10, 1999–2012, doi:10.3762/bjoc.10.208

• been identified that affect the stability of RF. These factors include radiation source, its intensity and wavelength, pH, presence of oxygen, buffer concentration and ionic strength, solvent polarity and viscosity, and use of stabilizers and complexing agents. A detailed review of the literature in

• concentration (0.2–1.0 M) in the pH range of 4.0–7.0 (Figure 8). The trivalent citrate ions were found to have a greater inhibitory effect on the photolysis of RF as compared to the divalent citrate ions probably due to the quenching of the excited triplet state of RF [31]. Effect of solvent polarity and

• viscosity The rate of RF photolysis is affected by solvent polarity, which causes changes in the conformation of the ribityl side chain to undergo degradation [83]. RF shows higher photostability in less polar solvents [96]. When RF was irradiated anaerobically in alcohols and alcohol/water mixtures, a

cis–trans Isomerization of silybins A and B

• Michaela Novotná,
• Radek Gažák,
• David Biedermann,
• Florent Di Meo,
• Petr Marhol,
• Marek Kuzma,
• Lucie Bednárová,
• Kateřina Fuksová,
• Patrick Trouillas and
• Vladimír Křen

Beilstein J. Org. Chem. 2014, 10, 1047–1063, doi:10.3762/bjoc.10.105

• EtOAc) and acids (η = 7.3 eV in EtOAc), respectively (Table 2), favoring such a coordinate bond. The hardness of BF3 and silybin A is not significantly modified when the solvent polarity is increased (Table 2). The hardness of silybin B was not calculated, as the stereochemistry is not expected to

• study the impact of the solvent polarity on the HSAB principle. The hardness of BF3 and silybin A is not significantly modified when the solvent polarity is increased (Table 2). New methods to rationalize chemical reactivity have been developed in the field of quantum mechanical methods over the past

The Ugi four-component reaction as a concise modular synthetic tool for photo-induced electron transfer donor-anthraquinone dyads

• Sarah Bay,
• Gamall Makhloufi,
• Christoph Janiak and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 1006–1016, doi:10.3762/bjoc.10.100

• term of the solvent polarity and the effect of the distance of the donor and acceptor moieties according to Indeed, for all Do-anthraquinone dyads 8 exergonic Gibbs free energies for the electron transfer are found, both for the simplified free enthalpy ΔGET,simpl, i.e., the first two terms of