RESUMO
In order to obtain sulfur-containing organophosphorus compounds that are promising as extractants of heavy metals, the interaction of elemental phosphorus and sulfur with alkyl bromides catalyzed using strong bases was studied. According to the task, the reaction of non-toxic and non-flammable red phosphorus with alkyl bromides under conditions of phase transfer catalysts (PTC), followed by the introduction of elemental sulfur into the reaction medium, were studied. It is shown that alkyl bromides interact with red phosphorus when heated (95-105 °C, 5-8 h) under conditions of phase transfer catalysts (PTC) in a two-phase system: a 60% aqueous solution of KOH-toluene-benzyltriethylammonium chloride (BTEAC) forming a mixture of organophosphorus compounds along with alkylphosphines (57-60%), are the main reaction products; alkylphosphine oxides are also formed (40-43%). The introduction of elemental sulfur (solution in toluene) at the final stage of the process into the reaction mass cooled to 40-60 °C leads to the expected alkylphosphine sulfides, which are the result of the interaction of alkylphosphines with sulfur. The formation of complex mixtures of products prevents the release of target alkylphosphine sulfides in individual form. However, the synthesized mixture of alkylphosphine sulfides and alkylphosphine oxides without separation into individual components is promising for studying its extraction properties in relation to heavy metals. Testing of the extraction properties of synthesized mixtures of alkylphosphine sulfides and alkylphosphine oxides in relation to heavy metals (Ni, Co, Zn, Pb) and noble metals (Ag) showed that the resulting mixtures of tertiary phosphine oxides and phosphine sulfides are highly effective extractants. The degree of extraction in relation to Ni, Co, Zn, and Pb varies from 99.90 to 99.99%, and for Ag from 99.56 to 99.59%.
RESUMO
Long-chain n-alkyl-H-phosphinic acids (Alk = C4-C18) are chemoselectively synthesized in yields up to 90% via the direct one-pot alkylation/oxidation of red phosphorus (Pn) in the multi-phase alkyl bromide/KOH/H2O/toluene system with alkyl-PEG recyclable micellar catalysts, which demonstrate good recyclability.
RESUMO
Secondary phosphine chalcogenides react with primary amino alcohols under mild conditions (room temperature, molar ratio of the initial reagents 1 : 1) in a CCl4/Et3N oxidizing system to chemoselectively deliver amides of chalcogenophosphinic acids with free OH groups. Under similar conditions, mono-cross-coupling between secondary phosphine chalcogenides and 1,2- or 1,3-aminophenols proceeds only with the participation of phenolic hydroxyl to give aminophenylchalcogenophosphinic O-esters. The yields of the synthesized functional amides or esters are 60-85%.
RESUMO
Sulfur-containing pyrroles (1-3), tris(2-pyridyl)phosphine(selenide) sulfide (4-5) and 4-benzyl-6-(thiophen-2-yl)pyrimidin-2-amine (6) were synthesized and characterized by elemental analysis, IR and NMR spectra. In this study, the synthesized compounds of nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds (1-6) were evaluated against the human erythrocyte carbonic anhydrase I, and II isoenzymes, acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and α-glycosidase enzymes. The synthesized heterocyclic compounds showed IC50 values in range of 33.32-60.79 nM against hCA I, and 37.05-66.64 nM against hCA II closely associated with various physiological and pathological processes. On the other hand, IC50 values were found in range of 13.13-22.21 nM against AChE, 0.54-31.22 nM against BChE, and 13.51-26.55 nM against α-glycosidase as a hydrolytic enzyme. As a result, nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds (1-6) demonstrated potent inhibition profiles against indicated metabolic enzymes. Therefore, we believe that these results may contribute to the development of new drugs particularly in the treatment of some global disorders including glaucoma, Alzheimer's disease and diabetes.
Assuntos
Acetilcolinesterase/química , Butirilcolinesterase/química , Inibidores de Glicosídeo Hidrolases/química , Compostos Heterocíclicos/síntese química , Nitrogênio/química , Fósforo/química , Selênio/química , Compostos Heterocíclicos/química , Humanos , Relação Estrutura-AtividadeRESUMO
Quinolines undergo catalyst-free double CH-functionalization upon treatment with secondary phosphine oxides (70-75 °C, 20-48 h) followed by oxidation of the intermediate 2,4-bisphosphoryltetrahydroquinolines with chloranil. The yields of the target 2,4-bisphosphorylated quinolines are up to 77%. Thus, a double-SNHAr reaction sequence in the same molecule of quinoline has been realized. In the case of 2,4-bisphenylphosphoryltetrahydroquinolines, the aromatization occurs with elimination of one molecule of diphenylphosphine oxide to afford the products of monofunctionalization, 4-diphenylphosphorylquinolines, in 40-45% yields.
RESUMO
Quinolines react with acylacetylenes and secondary phosphine chalcogenides at 20-75 °C to afford N-acylvinyl-2(1)-chalcogenophosphoryldihydroquinolines in good and excellent yields. Unlike the pyridine-derived similar intermediates, which eliminate E-alkenes to give aromatic chalcogenophosphorylpyridines, thereby completing SNHAr reaction, with quinolines, the reaction stops at the formation of the above phosphorylated N-acylvinyl-dihydroquinolines, thus representing a pendant SNHAr process. This reaction opens a one-pot atom-economic single-step access to pharmaceutically targeted phosphorylated functionalized dihydroquinolines and isoquinolines.
RESUMO
Acridine adds secondary phosphine chalcogenides HP(X)R2 (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70-75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61-94% yields. This contrasts with pyridines, which under similar conditions undergo an SNHAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the SNHAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil.
RESUMO
Pyridines undergo site selective cross-coupling with secondary phosphine chalcogenides (oxides, sulfides, and selenides) in the presence of acylphenylacetylenes under metal-free mild conditions (70-75 °C, MeCN) to afford 4-chalcogenophosphoryl pyridines in up to 71% yield. In this new type of SNHAr reaction acylacetylenes act as oxidants, being stereoselectively reduced to the corresponding olefins of the E-configuration.
RESUMO
Secondary phosphine oxides react with vinyl sulfides (both alkyl- and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7-30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides in 70-93% yields.
RESUMO
Dinuclear gold(i) dithio- and diselenophosph(in)ate complexes were prepared to serve as precursors for subsequent oxidative addition (OA) chemistry following reaction with mild oxidant iodine, I2. The new OA products circumvented the formation of the expected dinuclear Au(ii) complexes, but instead formed novel chelating mononuclear square-planar gold(iii) products of the type [AuI2{E2PR2}] (R = (CH2)2Ph; E = S, 2; E = Se, 3) and [AuI2{Se2P(OR)2}] (R = Et, 4; (i)Pr, 5) directly. We further demonstrate that this process is chemically reversible as all the Au(iii) complexes undergo chemical reductive elimination to the starting dinuclear Au(i) complexes in the presence of SnI2 as determined by (119)Sn and (31)P NMR. The complexes (2-5) were all prepared from the reaction between I2 and the corresponding dinuclear gold(i) precursor material. All new complexes were characterized by (1)H, (31)P, (77)Se (for E = Se) NMR, infrared spectroscopy, elemental analysis and single crystal X-ray diffraction.
RESUMO
Theoretical energy-based conformational analysis of bis(2-phenethyl)vinylphosphine and related phosphine oxide, sulfide and selenide synthesized from available secondary phosphine chalcogenides and vinyl sulfoxides is performed at the MP2/6-311G** level to study stereochemical behavior of their (31)P-(1)H spin-spin coupling constants measured experimentally and calculated at different levels of theory. All four title compounds are shown to exist in the equilibrium mixture of two conformers: major planar s-cis and minor orthogonal ones, while (31)P-(1) H spin-spin coupling constants under study are found to demonstrate marked stereochemical dependences with respect to the geometry of the coupling pathways, and to the internal rotation of the vinyl group around the P(X)-C bonds (X = LP, O, S and Se), opening a new guide in the conformational studies of unsaturated phosphines and phosphine chalcogenides.