SeOCl2 Research Articles

Synthesis of Se-polysaccharide mediated by selenium oxychloride: Structure features and antiproliferative activity

Selenium oxychloride (SOC) was employed as a highly reactive selenide reagent to synthesize selenized Artemisia sphaerocephala polysaccharides (SeASP). Se content of SeASP was significantly increased (∼22,400 μg/g) as compared to HNO3/H2SeO3 selenylation method (1703 μg/g). Furthermore, selenized ASP was prepared by using microwave-assisted synthesis which obviously enhanced selenylation kinetics. FT-IR, Raman, XPS and NMR results exhibited seleno-group was substituted at C6 position in the form of selenite (Se4+). SEC-MALLS suggested SOC system could effectively avoid the degradation of polysaccharide chain. Meanwhile, MALLS calculation, MB spectrophotometric method and AFM observation showed SeASP appeared spherical and rod-shaped conformation after selenylation. Seleno-groups were more likely to affect the conformational transformation of polysaccharide chains. Moreover, SeASP could significantly enhance antiproliferative activity against three tumor cells, of which the IC50 value of HepG2 was calculated as 24.35 μg/mL. It was found that higher Se content could effectively improve the antitumor activities of Se-polysaccharides in vitro.

Optimization of selenylation modification for garlic polysaccharide based on immune-enhancing activity

Garlic polysaccharide (GPS) was modified in selenylation respectively by nitric acid-sodium selenite (NA-SS), glacial acetic acid-selenous acid (GA-SA), glacial acetic acid-sodium selenite (GA-SS) and selenium oxychloride (SOC) methods each under nine modification conditions of L9(34) orthogonal design and each to obtain nine selenizing GPSs (sGPSs). Their structures were identified, yields and selenium contents were determined, selenium yields were calculated, and the immune-enhancing activities of four sGPSs with higher selenium yields were compared taking unmodified GPS as control. The results showed that among four methods the selenylation efficiency of NA-SS method were the highest, the activity of sGPS5 was the strongest and significantly stronger than that of unmodified GPS. This indicates that selenylation modification can significantly enhance the immune-enhancing activity of GPS, NA-SS method is the best method and the optimal conditions are 0.8:1 weight ratio of sodium selenite to GPS, reaction temperature of 70°C and reaction time of 10h.

Photoelectron Spectroscopy and Ionic Fragmentation of OSeCl2 and Its Analogue OSCl2 under VUV Irradiation.

The electronic structure and the dissociative ionization of selenium oxychloride, OSeCl2, have been investigated in the valence region by using results from both photoelectron spectroscopy (PES) and synchrotron-based photoelectron photoion coincidence (PEPICO) spectra. The PES is assigned with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) and symmetry adapted cluster/configuration interaction (SAC-CI) levels. The first energy ionization is observed at 11.47 eV assigned to the ionization of electrons formally delocalized over the Se, Cl, and O lone pair orbitals. Irradiation of OSeCl2 with photons in the valence region leads to the formation of OSeCl2(•+), OSeCl(+), SeCl2(•+), SeCl(+), and SeO(•+) ions. Furthermore, the inner shell Se 3p, Cl 2p, and Se 3s electronic regions of OSeCl2 together with S 2p, Cl 2p, and S 2s electronic regions of thionyl chloride, OSCl2, have been studied by using tunable synchrotron radiation. Thus, total ion yield spectra and the fragmentation patterns deduced from PEPICO spectra at the various excitation energies have been studied. Cl(+), O(•+), and Se(•+) ions appear as the most intense fragments in the OSeCl2 PEPICO spectra, like in the sulfur analogue OSCl2, whose photofragmentation is dominated by the Cl(+), O(•+), and S(•+) ions. Fragmentation processes in OSCl2 leading to the formation of the double coincidences involving atomic ions appear as the most intense in the PEPIPICO spectra.

Preparation of a Novel Organoselenium Compound and Its Anticancer Effects on Cervical Cancer Cell Line HeLa

This study aims at developing new organoselenium compounds with good anticancer ability and low biotoxicity. Sucrose selenious ester (sucrose-Se) was synthesized by the reaction between sucrose and selenium oxychloride. MTT assay showed that sucrose-Se effectively inhibited the proliferation of cervical cancer cell line HeLa in a dose-dependent manner without cytostatic influence on human normal liver cell line HL-7702. Morphological observation and agarose gel electrophoresis demonstrated that sucrose-Se induced apoptosis to HeLa cells. In addition, sucrose-Se was able to inhibit proliferation of bladder carcinoma cell line 5637, human malignant melanoma cell line A375, and gastric carcinoma cell line MGC-803. Median lethal dose of sucrose-Se and sodium selenite was 290.0 and 13.1 ppm, respectively, in the acute toxicity test on mice. In conclusion, sucrose-Se has potential in cancer chemoprevention due its apoptosis induction capacity and low biotoxicity.

A new layered indium selenium oxychloride material: Synthesis, structure, and characterization of InSeO 3Cl

A new layered indium selenium oxychloride material, InSeO 3Cl has been synthesized by a standard solid-state reaction using In 2O 3, InCl 3, and SeO 2 as reagents. Single-crystal X-ray diffraction was used to determine the structure of the reported material. InSeO 3Cl crystallizes in the orthorhombic space group Pbca (No. 61), with a = 7.0580(14) Å, b = 7.0390(14) Å, c = 16.206(3) Å, V = 805.1(3) Å 3, and Z = 8. InSeO 3Cl has a layered structure consisting of distorted InO 4Cl 2 octahedra and SeO 3 polyhedra. The Se 4+ cations are in asymmetric coordination environment attributed to their stereoactive lone pairs. The lone pairs on the Se 4+ cations approximately point in the [101], [−10-1], [10-1], and [−101] direction. A separation of the halophile and the chalcophile moieties is observed from the reported material. Detailed structural analysis with full characterization including infrared spectroscopy, bond valence calculations, thermogravimetric analysis, elemental analysis, and dipole moment calculations are reported.

Hydrothermal synthesis and crystal structure of ErSeO 3Cl

A new erbium–selenium oxychloride, ErSeO 3Cl, has been synthesized hydrothermally starting from ErCl 3·6H 2O and SeO 2 in LiCl aqueous solution, and its crystal structure solved from single-crystal X-ray diffraction data. ErSeO 3Cl crystallizes in the HoTeO 3Cl structure type in the orthorhombic system, space group Pnma (No. 62), with the cell parameters a=7.185(1) A ̊ , b=6.890(1) A ̊ , c=8.720(2) A ̊ , V=431.7(1) A ̊ 3 , Z=4. The structure was refined to R1=0.0259, w R2=0.0648 for 35 variables and 508 unique reflections. The 3D structure of ErSeO 3Cl is formed from linked ErO 5Cl 2 polyhedra and SeO 3E (E—lone electron pair) polyhedra. We compare the crystal structure of ErSeO 3Cl with the structures of other known rare-earth (Bi)–Se(Te) oxyhalides of the common formula MChO 3 X ( M= Ln(Bi), Ch=Se, Te, X=Cl, Br, I).

Expeditious synthesis of new 1,2,3-thiadiazoles and 1,2,3-selenadiazoles from 1,2-diaza-1,3-butadienes via Hurd-Mori-type reactions.

Alpha-substituted hydrazones obtained from 1,2-diaza-1,3-butadienes and methylenic or methinic activated substrates gave rise to a wide range of cyclic compounds. In particular, in the presence of thionyl chloride as solvent-reagent, they were transformed into 1,2,3-thiadiazoles,(1) with selenium oxychloride in new 4-substituted 2,3-dihydro-1,2,3-selenadiazoles, while with selenium dioxide, they were transformed into 4-substituted 1,2,3-selenadiazoles. We have also examined the nucleophilic behavior of 1,2,3-thiadiazole 4a in the reaction with 1,2-diaza-1,3-butadienes that produced, under basic conditions, 4-hydrazono-1-(1,2,3-thiadiazolyl)pentane derivatives. This event represents an interesting example of stereoselective synthesis because it leads exclusively to the formation of the RR/SS racemic mixture. These latter compounds, treated with thionyl chloride, gave the corresponding 1,3-di-1,2,3-thiadiazolylpropane derivatives, while with sodium methoxide they afforded 1,2,3-thiadiazolyl-2-oxo-2,3-dihydro-1H-pyrrole systems.

Condensed Thiophenes and Selenophenes: Thionyl Chloride and Selenium Oxychloride as Sulfur and Selenium Transfer Reagents.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Condensed Thiophenes and Selenophenes: Thionyl Chloride and Selenium Oxychloride as Sulfur and Selenium Transfer Reagents

3,4-Cyanomethyl substituted thiophenes reacted with thionyl chloride in the presence of base to give dicyano substituted thieno(3,4-c)thiophenes. The use of selenium oxychloride furnished the corresponding cyano substituted seleno(3,4-c)thiophene. 1,2-Phenylenediacetonitriles gave the corresponding cyano substituted benzo(c)thiophenes and benzo(c)selenenophenes, respectively, upon reaction with thionyl chloride and selenium oxychloride in the presence of base.

Oxidative addition of seleninyl chloride to Vaska's complex

The reaction of Vaska's complex [IrCl(CO)(PPh 3) 2] with seleninyl chloride (SeOCl 2) provided the complex [IrCl 2(SeOCl)(CO)(PPh 3) 2], photolysis of which led to extrusion of ‘SeO’ and formation of [IrCl 3(CO)(PPh 3) 2].

Benzotris[1,2,5]thiadiazol in einer Eintopfreaktion aus Benzolhexamin

Benzotris[1,2,5]thiadiazole in a One‐Pot Reaction from BenzenehexamineCondensation of benzenehexamine (1) with thionyl chloride in the presence of pyridine gave the title compound 2 (69% yield) in a one‐pot reaction. A similar reaction of 1 with seleninyl chloride or an alternative condensation of 1 with selenium dioxide led to the analogous selenium heterocycle 3 in traces only.

ChemInform Abstract: Syntheses with Diketo Selenides.

AbstractThe ketones (I) react with selenium oxychloride (II) to give the diketo selenide dichlorides (III) which are reductively dechlorinated with Na2S2O4 to yield the diketo selenides (IV).

ChemInform Abstract: A Seleno‐Pummerer Rearrangement of Haloselenuranes.

AbstractThe methyl ketones (I) react with selenium oxychloride (II) to form the di(acylmethyl)selenium dichlorides (III) which are rearranged upon treatment with triethylamine or heating to give the acylmethyl acylchloromethyl selenides (IV).

ChemInform Abstract: A Novel Synthesis of Selenophenes.

AbstractThe ketones (I) react with selenium oxychloride (II) to give the selenides (IV) after reductive dehalogenation.

ChemInform Abstract: Preparation and Crystal Structures of Tetracyanoquinodimethans Fused with (1,2,5)Selenadiazole Units.

AbstractThe diaminobenzothiadiazole derivative (IIb), prepared from 1,4‐dimethoxybenzene (I) by known methods, is cyclized with selenium oxychloride (III) to produce the quinone (IV).

ChemInform Abstract: Seleninyl Chloride as an Active Chlorinating Reagent.

AbstractSeleninyl chloride (III), prepared from selenium dioxide and trimethylchlorosilane, is used as a chlorinating agent for citronellyl acetate (V), (VI), or isoprene (IX), giving the chlorinated products (VII) and (VIII) or (X) and (XI).

ビス（パラメトキシフェニル）セレノキシド

Bis (p-methoxyphenyl) selenoxide, readily available from anisole and selenium dioxide or selenium oxychloride, is of practical use as a tractable and versatile oxidizing agent. Thus it can be used for mild oxidations of thiol to disulfide, sulfide to sulfoxide, hydroquinone to p-benzoquinone, catechol to o-benzoquinone, phosphine to phoshine oxide, benzoylhydrazine to sym- dibenzoylhydrazine, phenylhydroxylamine to azoxybenzene, and benzoin to benzil. Its specific reactivity is demonstrated by a useful conversion of thioamides involving thioureas into 1, 2, 4-thiadiazoles. In particular, polymer-supported analogous selenoxide effects novel solvent-dependent reactions toward thioamides. In addition, the title selenoxide has potential applicability such as an effective reagent for Kornblum reaction, a cooxidant for catalytic SeO2 oxidation, and a mediator for electrochemical oxidation.

Selenium oxychloride as an effective chlorinating agent and solvent for vanadium(IV) complexes. An ESR study

On discute de la chloruration efficace par SeOCl 2 des complexes dimeres et monomeres d'oxovanadium (IV) et les proprietes de SeOCl 2 comme solvant des complexes de dichloro-V (IV)

Synthesis of 2,3,7,8‐tetramethoxydibenzotellurophene and its thio and seleno analogues

AbstractThe title compounds 5 were obtained from the reaction of 3,3′,4,4′‐tetramethoxybiphenyl (6) or its 2,2′‐dilithio derivative 8 with various chalcogen electrophiles (sulfur dichloride, selenium tetrachloride, selenium oxychloride and tellurium tetrachloride).

ChemInform Abstract: THE REACTIONS OF PHENYLMAGNESIUM HALIDES WITH SELENINYL CHLORIDE, DIPHENYL SELENOXIDE, AND DIBROMODIPHENYLSELENIUM

AbstractDurch Reaktion von Seleninylchlorid mit Phenylmagnesiumhalogeniden und nachfolgende Hydrolyse mit wäßriger HBr wurde die Triphenylselenoniumverbindung (I) neben (II) und (III) dargestellt, deren Ausb. stark von dem molaren Verhältnis der Reaktanten und die Art des Halogens beeinflußt wird.