The First Example of the Friedel-Crafts Cyclization Leading to (10-Hydroxy-9,10-dihydroanthr-9-yl)phosphonium Salts without the Expected Bradsher Dehydration.

The reaction of (acetalaryl)arylmethanols with various phosphines PRRR (R = R = R = Ph; R = R = Ph, R = Me and R = R = Me, R = Ph) under acidic conditions (e.g., HCl, HBF, TsOH) unexpectedly led to the formation of (10-hydroxy-9,10-dihydroanthr-9-yl)phosphonium salts instead of the corresponding anthryl phosphonium salts.

New Perspectives for Antihypertensive Sartans as Components of Co-crystals and Co-amorphous Solids with Improved Properties and Multipurpose Activity.

Sartans (angiotensin II receptor blockers, ARBs), drugs used in the treatment of hypertension, play a principal role in addressing the global health challenge of hypertension. In the past three years, their potential use has expanded to include the possibility of their application in the treatment of COVID-19 and neurodegenerative diseases (80 clinical studies worldwide). However, their therapeutic efficacy is limited by their poor solubility and bioavailability, prompting the need for innovative approaches to improve their pharmaceutical properties.

Can Pharmaceutical Excipients Threaten the Aquatic Environment? A Risk Assessment Based on the Microtox Biotest.

The ecotoxicological impact of pharmaceuticals has received considerable attention, primarily focusing on active pharmaceutical ingredients (APIs) while largely neglecting the potential hazards posed by pharmaceutical excipients. Therefore, we analyzed the ecotoxicity of 16 commonly used pharmaceutical excipients, as well as 26 API-excipient and excipient-excipient mixtures utilizing the Microtox test. In this way, we assessed the potential risks that pharmaceutical excipients, generally considered safe, might pose to the aquatic environment.

-Acetals in a New Modification of -Friedel-Crafts-Bradsher Cyclization-Synthesis of Fluorescent (Hetero)acenes and Mechanistic Considerations.

This paper presents the use of -acetals in a new modification of the -Friedel-Crafts-Bradsher cyclization. In this reaction, under mild reaction conditions (25 °C), three- and four-ring fused -acenes (major) and/or -acenes (minor) are formed, the latter products having never been observed before in this type of cyclization. In this way, two electronically different fluorophores could be obtained in a single cyclization reaction, one of them having strong electron donor properties (+M effect of alkoxy groups) and the other having donor-acceptor properties (+M and -I effects of the -group, Hammett's constants).

Comprehensive Review on Synthesis, Properties, and Applications of Phosphorus (P, P, P) Substituted Acenes with More Than Two Fused Benzene Rings.

This comprehensive review, covering the years 1968-2022, is not only a retrospective investigation of a certain group of linearly fused aromatics, called acenes, but also a presentation of the current state of the knowledge on the synthesis, reactions, and applications of these compounds. Their characteristic feature is substitution of the aromatic system by one, two, or three organophosphorus groups, which determine their properties and applications. The (P, P, P) phosphorus atom in organophosphorus groups is linked to the acene directly by a P-C bond or indirectly through an oxygen atom by a P-O-C bond.

Organosulfur Materials with High Photo- and Photo-Oxidation Stability: 10-Anthryl Sulfoxides and Sulfones and Their Photophysical Properties Dependent on the Sulfur Oxidation State.

While few studies show only symmetrical and poorly mono-SO (n = 0-2) substituted acenes, in this study, we present a synthesis of a new group of unsymmetrical, significantly substituted derivatives, which revealed unique photophysical properties. Both sulfides (S), sulfoxides (SO) and sulfones (SO) showed very high photochemical stabilities, unusual for these groups, during UV-irradiation at 254/365 nm (air O and Ar), which was higher than any found in the literature. For the (S)/(SO) series (254 nm), the stabilities of 80-519 min.

Role of Hydrogen Bonds in Formation of Co-amorphous Valsartan/Nicotinamide Compositions of High Solubility and Durability with Anti-hypertension and Anti-COVID-19 Potential.

Physicochemical properties, in particular solubility and the associated bioavailability, are key factors in determining efficacy of poorly water-soluble drugs, which constitute 40% of new drugs in the market, and improving them is an important challenge for modern pharmacy. A recent strategy to achieve this goal is formation of stable co-amorphous solid dispersions with co-formers of low molecular weight. Here, the amorphization strategy was applied for low-soluble anti-hypertensive valsartan (VAL), an angiotensin II receptor blocker, and nicotinamide, which exhibits lung- and cardio-protective effects.

The -Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials.

The interest in functional materials possessing improved properties led to development of new methods of their synthesis, which allowed to obtain new molecular arrangements with carbon and heteroatom motifs. Two of the classical reactions of versatile use are the Friedel-Crafts and the Bradsher reactions, which in the new heteroatomic versions allow to replace ring carbon atoms by heteroatoms. In the present work, we review methods of synthesis of C-S and C-P bonds utilizing - and -Friedel-Crafts-Bradsher cyclizations.

Modification of the Microtox® Basic Solid Phase Test: A new application for the ecotoxicological studies on poorly soluble antihypertensive drugs.

Increasing consumption of angiotensin II receptor blockers (ARBs: valsartan, losartan potassium, telmisartan) is inevitably associated with their appearance in the environment and impact on aquatic and terrestrial organisms. Since the pharmaceuticals do not occur as pure substances in the environment, but as complex mixtures with other active pharmaceutical ingredients (APIs) and excipients used in pharmaceutical formulations, we compared the ecotoxicity of ARBs in various forms: as pure APIs, in pharmaceutical formulations and in mixtures with hydrochlorothiazide (HCT). Because the studied APIs are poorly water-soluble, the Microtox® Basic Solid Phase Test, utilizing bacteria Aliivibrio fischeri, has been modified by using a neutral matrix.

Ecotoxicity of ammonium chlorophenoxyacetate derivatives towards aquatic organisms: Unexpected enhanced toxicity upon oxygen by sulfur replacement.

Phenoxyacetate herbicides, such as 2,4-D and MCPA, having a high toxicity to non-target organisms are commonly used for controlling broadleaf weeds in agriculture. However, novel and environmentally friendly analogs are constantly sought after. For this purpose, various substituents at the phenyl group have been tested to find the optimal balance between the potent herbicidal activity and safety for non-target species.

Ultrasound-assisted synthesis of RO- and RS-substituted (hetero)acenes via oxo- and thio-Friedel-Crafts/Bradsher reactions.

Two heteroatom-variants of the Friedel-Crafts/Bradsher cyclization of o-acetalaryl(aryl)methyl ethers and o-dithioacetalaryl(aryl)methyl thioethers, have been realized with the ultrasound assistance. The environmentally friendly "oxo-variant" (Oxo-F-C/B), proceeding in a medium containing mineral acid and a large amount of water (HCl/CHCN) led to a very efficient formation of RO-substituted (hetero)acenes in less than 5 min. In the "thio-variant" (Thio-F-C/B), o-dithioacetalaryl(aryl)methyl thioethers underwent ultrasound-assisted cyclization in nonaqueous medium (FeCl/KI/EtOH) in less than 25 min.

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel-Crafts/Bradsher Cyclization Reaction.

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T =331-354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60-70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core.

Ammonium haloacetates - An alternative to glyphosate?

This study shows the design, synthesis and evaluation of eco(phyto)toxic and herbicidal activities of quaternary ammonium salts (QASs), derived from haloacetic acids, in context of the search for safer alternatives to the commonly used herbicide, N-(phosphonomethyl)glycine (glyphosate). The structure of the investigated QASs refers to the heteroatom sequence in the anion of glyphosate in which the (P-C)-N nitrogen atom was replaced by one or more halogens (F, Cl). The ecotoxicity of the synthesized QASs was tested against luminescent marine bacteria Vibrio fischeri (Microtox test) and the crustaceans Heterocypris incongruens (Ostracodtoxkit F™).

Total synthesis of (±)-epithuriferic acid methyl ester via Diels-Alder reaction.

In this paper, we have described the first total synthesis of (±)-epithuriferic acid methyl ester from non-natural sources, in four steps (20% overall yield). The key step involves the Diels-Alder reaction of isobenzofuran with methyl 3-(dimethoxyphosphoryl)acrylate which is controlled by "ortho" regio- and endo stereoselectivities due to the COOMe group.

Catalyzed hydrogenation of condensed three-ring arenes and their N-heteroaromatic analogues by a bis(dihydrogen) ruthenium complex.

A series of anthracene and acridine derivatives were hydrogenated under mild reaction conditions (80 °C, 3 bar of H(2)) using the bis(dihydrogen) complex [RuH(2)(η(2)-H(2))(2){P(C(6)H(11))(3)}(2)] (1) as a catalyst precursor. The influence of a methyl substituent on the substrate was studied. In all our systems, hydrogenation was only observed at the external rings leading to the corresponding 4H- or 8H-derivatives of anthracene and acridine.

Synthesis and optoelectronic properties of hexahydroxylated 10-O-R-substituted anthracenes via a new modification of the Friedel-Crafts reaction using O-protected ortho-acetal diarylmethanols.

A new modification of the Friedel-Crafts type intramolecular cyclization involving O-protected ortho-acetal diarylmethanols as a new type of reactant, was carried out for the first time in a medium containing a large amount of water at room temperature and enabled synthesis of a series of electron-rich, hexahydroxylated 10-O-R-substituted anthracenes, where R is an alkyl (Me, nBu, n-C(16)H(33)) or arylalkyl group (CH(2)Ph, CH(2)-2-Napht, CH(2)C(6)H(4)CH(2)OAr) and also evaluation of their electronic and optoelectronic properties in solution, crystal, and solid thin film. In this transformation, a central 10-O-R-substituted benzene ring was formed, fused to rings originating from two independent aromatic aldehydes. The reaction proceeded via two identified mechanisms involving acetal and/or free aldehyde groups.

1-(Thiophen-3-yl)ethanone.

The structure of the title compound, C(6)H(6)OS, exhibits a flip-type disorder of the thiophene ring [occupancy ratio = 0.848 (3):0.152 (3)], which is typical for many thiophene derivatives.

La4.27Mg2.89Zn30, a new structure type with strong positional disorder.

Ternary tetralanthanum trimagnesium tricontazinc, La(4.27)Mg(2.89)Zn(30), crystallizes as a new structure type.

The new ternary phases of La3(Zn0.874Mg0.126)11 and Ce3(Zn0.863Mg0.137)11.

The new ternary intermetallic title compounds, namely trilanthanum undeca(zinc/magnesium), La(3)(Zn(0.874)Mg(0.126))(11), (I), and tricerium undeca(zinc/magnesium), Ce(3)(Zn(0.

First approach to nitrogen-containing fused aromatic hydrocarbons as targets for organoelectronics utilizing a new transformation of O-protected diaryl methanols.

A new concise approach for the construction of heteroatom analogues of polycyclic aromatic benzo[g]quinoline, benzo[b]carbazole, and pyrido[b]carbazole systems via diaryl methanols is described. This transformation involves formation of a central benzene ring fused to two aromatic 5- or 6-membered rings of pyrrole and/or pyridine by using a combination of two aromatic aldehydes, of which at least one contains a ring nitrogen. Analysis of the UV and fluorescent properties, Stokes shifts, quantum yields in solution, and pi-stacking interactions in the crystal structures of the new materials was performed.

One-pot tandem 1,4-1,2-addition of phosphites to quinolines.

Trialkyl and silylated dialkyl phosphites were evaluated as phosphorus nucleophiles for the addition to quinolines in a strong acidic medium allowing consecutive 1,4- and 1,2-addition breaking up the aromatic stabilisation, thereby leading to 2,4-diphosphono-1,2,3,4-tetrahydroquinolines in one single reaction step in moderate to good yields (2-84%).

4-Methoxy-1-naphthol: chains formed by O-H...O hydrogen bonds and pi-pi stacking interactions.

The structure of 4-methoxy-1-naphthol, C(11)H(10)O(2), (I), contains an intermolecular O-H...

5-Amino-1-naphthol: two-dimensional sheets built up from R(4)(4)(18) rings formed by O-H...N, N-H...O and pi-pi interactions.

The crystal structure of the title compound, C(10)H(9)NO, (I), contains intermolecular O-H...

4-Chloro-1-naphthol.

Molecules of the title compound, C(10)H(7)ClO, (I), are connected by a single strong O-H...