Dipole moments of some diphenyl thioethers: Absolute conformation of bis(o-nitrophenyl) sulphide

The electric dipole moments of three diphenyl thioethers have been measured in benzene solution at 25· and the conformational analysis of bis(o-nitrophenyl) sulphide has been carried out by vector addition. The results show that this compound exists in a twisted conformation with the phenyl rings considerably rotated from coplanarity with respect to the C-S-C plane and indicate that in o,o′-disubstituted derivatives of diphenyl sulphide steric rather than conjugative effects operate in determining the conformational preference.     

Bis(4-methylpiperidine-1-carbodithioato)-lead(II) and Bis(4-benzylpiperidine-1-carbodithioato)-lead(II) as Precursors for Lead Sulphide Nano Photocatalysts for the Degradation of Rhodamine B

Bis(4-methylpiperidine-1-carbodithioato)-lead(II) and bis(4-benzylpiperidine-1-carbodithioato)-lead(II) were prepared and their molecular structures elucidated using single crystal X-ray crystallography and spectroscopic techniques. The compounds were used as precursors for the preparation of lead sulphide nano photocatalysts for the degradation of rhodamine B. The single crystal structures of the lead(II) dithiocarbamate complexes show mononuclear lead(II) compounds in which each lead(II) ion coordinates two dithiocarbamato anions in a distorted tetrahedral geometry. The compounds were thermolyzed at 180 ℃ in hexadecylamine (HDA), octadecylamine (ODA), and trioctylphosphine oxide (TOPO) to prepare HDA, ODA, and TOPO capped lead sulphide (PbS) nanoparticles. Powder X-ray diffraction (pXRD) patterns of the lead sulphide nanoparticles were indexed to the rock cubic salt crystalline phase of lead sulphide. The lead sulphide nanoparticles were used as photocatalysts for the degradation of rhodamine B with ODA-PbS1 achieving photodegradation efficiency of 45.28% after 360 min. The photostability and reusability studies of the as-prepared PbS nanoparticles were studied in four consecutive cycles, showing that the percentage degradation efficiency decreased slightly by about 0.51–1.93%. The results show that the as-prepared PbS nanoparticles are relatively photostable with a slight loss of photodegradation activities as the reusability cycles progress.     

Thermal oxidation and molding feasibility of cycloolefin copolymers (COCs) with high glass transition temperature

Cycloolefin copolymers (COCs) with high glass transition temperature (T_g = 203 °C) have been synthesized and pelletized by extrusion molding. However, their colors change from transparent to yellow during extrusion molding because of thermal oxidation and generation of alkene groups. We have successfully blended several antioxidants (Irganox 1010, Irgafos 168, Irganox HP2225 and Irganox HP2921) into lab-made COCs to avoid the discoloration. The experimental results show that Irganox HP2921 is the best antioxidant among the antioxidants used and can effectively not only suppress thermal oxidation but also eliminate the color stain.     

Measurement and correlation of solid–liquid equilibria of Irganox 1010 with n-hexane

Solid–liquid equilibria (SLE) for the binary mixtures of Irganox 1010 with n-hexane have been measured using a method in which an excess amount of solute was equilibrated with the alkane solution. The liquid concentrations of the Irganox 1010 in the saturated solution were analyzed by UV spectrometry. Activity coefficients for Irganox 1010 have been calculated by means of the Wilson, NRTL and UNIQUAC models and with them were correlated solubility data that were compared with the experimental ones. The best correlation of the solubility data has been obtained by the Wilson model, by which the average root-mean-square deviation of temperature for the system is 0.33 K.     

Direct synthesis of mixed methylethyllead alkyls

The reactions of lead oxide, sulphide, and chloride with a mixture of dimethyl- and diethyl-aluminium chloride in the presence of Lewis bases have been studied. Mixtures of methylethyllead compounds of the type Me_4-nPbEt_n (0 ? n ? 4) are formed.A reaction path is proposed.     

Sulphur compounds in the kerosine boiling range of middle east distillates Occurrence of a bicyclic thiophene and a thienyl sulphide

A bicyclic thiophene, 1,4,4-trimethyl-4,5,6,7-tetrahydroisothianaphthene, and a thienyl sulphide, methyl 3, 4, 5-trimethyl-2-thienyl sulphide, have been isolated from a concentrate of sulphur compounds obtained in the refining of a Middle East kerosine. The structures of these compounds have been established.     

Determination of antioxidants in polyolefins by pressurized liquid extraction prior to high performance liquid chromatography

The effect that a high amount of mineral filler might have on the extraction process of antioxidants from polyethylene and polypropylene was investigated. Extraction of Irganox 1010, Irganox 1076 and Irgafos 168, along with its oxidation product 2,4-di-tert-butylphenol, from freeze ground polyethylene–based (PE–based) and polypropylene–based (PP–based) mineral concentrates of 85 w/w calcium carbonate (CaCO₃) and 75 w/w talc was carried out by pressurized fluid extraction (PLE) prior to high performance liquid chromatography (HPLC). Results indicate that 85 w/w CaCO₃ did not affect the extraction process from PE or PP. For talc concentrates, additive recovery from PE and PP was considerably lower. The relation of recovery yield and mixing time was investigated for the talc concentrates and it was concluded that the presence of talc seemed to accelerate the rate of antioxidant consumption during sample processing, thus, less antioxidant was left to be extracted from the polyolefin; rather than talc has limited the extraction process. The method developed in this work has been applied to determine these compounds in several commercial samples.     

TMP与受阻酚Irganox 1010在异辛烷溶液中并用时光稳定作用的研究

本文研究了2,2,6,6-四甲基哌啶醇(简称TMP)和2,2,6,6-四甲基哌啶醇氮氧自由基(简称TMPO·)分别与四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(简称Irganox 1010)在异辛烷溶液中并用时的光稳定作用。结果表明:TMP与Irganox 1010的并用体系有反协同作用:Irganox 1010对异辛烷溶液的光氧化有敏化作用;TMP与Irganox 1010并用时,TMPO·的累积速率变慢,浓度极大值比只含TMP的样品低;TMPO·与Irganox 1010并用时,TMPO·的衰减比只含TMPO·的样品快得多。根据实验事实提出:TMPO·与Irganox 1010之间起了某种反应,该反应引起的氮氧自由基浓度的降低可能是受阻胺与受阻酚并用时产生反协同效应的主要原因。     

Influence of thiobisphenols on the photo-oxidation of low density polyethylene

The influence of thiobisphenols, some products of their thermo-oxidative transformation and model compounds on the photo-oxidation of low density polyethylene (Ld PE) has been studied. Thiobisphenols are found to have a pro-oxidant effect in the early period of exposure, which increases with their concentration. On the other hand, the carbonyl build up was retarded in a later irradiation period. Similar effects have been observed with some thiobisphenol transformation products, bis(3,5-di-tert. butyl-4-hydroxybenzyl) sulphide and its oxidation products, sulphoxide and sulphone, respectively, and model 4,4′-methylenebis(2-methyl-6-tert. butylphenol). Dodecyl 3,3′-thiodipropionate retarded the carbonyl build up during the whole period of ultraviolet irradiation. Kinetic data show that a concentration of 0·1% by weight of thiobisphenols is the most effective in retarding the carbonyl build up in Ld PE films. The formation of non-alcoholic oxygenated structures seems to be a specific effect of the sulphur containing compounds under study.     

Bisthiourea: thermal and structural investigation

Bisthiourea derivatives 1,1′-(ethane-1,2-diyl)bis(3-phenylthiourea), 1,1′-(propane-1,3-diyl)bis(3-phenylthiourea), and 1,1′-(butane-1,4-diyl)bis(3-phenylthiourea) have been synthesized and characterized by IR, ¹H NMR, and ¹³C NMR. Suitable crystals of 1,1′-(propane-1,3-diyl)bis(3-phenylthiourea) were grown for single-crystal X-ray analysis and from the data it was observed that they organize into the P-1 space group. The thermal decomposition of these compounds has been studied by TG–DSC.     

New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitro- and 1-chloro-2,6-dinitrobenzenes

New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitrobenzene and 1-chloro-2,6-dinitrobenzene were prepared from the corresponding bis(4-chloro-3-nitrophenyl)disulfide and bis(4-chloro-3,5-dinitrophenyl)disulfide, respectively. The SF₅ derivatives were obtained by fluorination of the disulfides with AgF₂ according to Sheppard’s method, while perfluoroalkylation was carried out by means of thermolytic reactions with xenon(II) bis(perfluoroalkylcarboxylates). The introduction of fluorine-containing, electron-withdrawing substituents into the aromatic ring (in the presence of other deactivating groups) reinforces the activation of the halogen substituent towards nucleophilic attack. Several nucleophilic substitution reactions have been carried out with these compounds, and as a result, some N- and S-containing groups were introduced in the benzene ring. For example, the previously unknown SF₅, CF₃S, and C₂F₅S analogues of trifluralin (Treflan^®) were prepared and characterized. Additional synthetic possibilities for heterocyclic chemistry are presented on the basis of reactions of the new 1-chloro-2,6-dinitrobenzene derivatives with ethyl thioglycolate wherein fluorine-containing derivatives of benzothiazole N-oxide were obtained as the main products.     

Photo-stabilising action of metal chelate stabilisers in polypropylene: Part VII—Additive interactions

The interactions of three metal chelates (nickel (II) 2,2′-thiobis (4-tertoctyl-phenolato), n-butylamine (Cyasorb UV 1084) and the nickel and calcium derivatives of bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate (Irgastab 2002 and Irganox 1425)) with other commercial additives, in the stabilisation of polypropylene film, are examined using normal and second-order derivative ultraviolet and infra-red spectroscopic techniques. It is shown that the observed behaviour is dependent on the particular additive, the processing history of the polymer and the metal chelate concerned, and is therefore highly complex. All three chelates show antagonism with a hindered piperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770), in unprocessed polymer, whereas one of the chelates behaves synergistically with this additive in processed samples. The chelates also show antagonism with a primary antioxidant, tris((3-(3′,5′-di-tert-butyl-4-hydroxybenzyl)-2′'-aceto-ethyl)) isocyanurate (Goodrite 3125), whereas, with a secondary antioxidant, distearyl pent-aerithrityl diphosphite (Weston 618), their behaviour is synergistic in both unprocessed and processed polymer. Two of the chelates show synergism with 2-hydroxy-4-n-octoxybenzophenone (Cyasorb UV 531), the remaining chelate showing antagonism. Mixtures containing a three-additive system show a more complex behaviour. The results are explained in terms of hydroperoxide decomposition, inhibition, stabiliser dispersion, ultraviolet stability and additive compatibility.     

Bialkyls from dialkylmetals I. Photochemistry and mass spectra of some (2-cyanoethyl)- and [2-(methoxycarbonyl)ethyl]metals

We have studied the photolysis and the fragmentation in the mass spectrometer of bis(2-cyanoethyl)mercury, bis(2-cyanoethyl) selenide, bis(2-cyanoethyl) sulphide, dibutylbis(2-cyanoethyl)stannane, and bis[2-(methoxycarbonyl)ethyl] selenide. The mercury compound gave a high yield of adiponitrile on photolysis and in the mass spectrometer it gave the fragmentation pattern of adiponitrile, including the molecular ion, as part of the total fragmentation pattern. A low yield of bialkyl was also formed on photolysis of the bis[2-(methoxycarbonyl)ethyl] selenide but no peaks corresponding to biakyl were observed in the mass spectrum. None of the other compounds yielded alkyl dimer.

A preliminary discussion of the results in terms of orbital symmetry is presented.     

Study of non-conjugated bichromophores linked by a polyether chain. Kinetic analysis of the formation of intramolecular excimers and photocyclomerization of some bisanthracenes

Dynamic properties of polyoyethylene chains are evaluated by the determination of rate constants (k_DM) of intramolecular excimer formation for four bis(9-anthryloxy)polyoxaalkanes in benzene and ethanol. The Kinetic parameters for the photodimenzation process of these compounds have been determined.     

Palladium-catalyzed arylation of bis(4-bromo-2-methylinden-1-yl)dimethylsilane and related compounds

A new procedure was developed for the synthesis of a broad range of ansa-zirconocenes containing bis(2-methyl-4-arylindenyl)dimethylsilane ligands. The method is based on the palladium-catalyzed reaction of halogen-substituted bis(indenyl)dimethylsilanes with various organozinc compounds. The aryl-substituted bridging ligands thus prepared serve as the starting compounds for the synthesis of ansa-zirconocenes, which can be used as components of promising catalysts for propylene polymerization.     

Photo-stabilising action of metal chelate stabilisers in polypropylene: Part V—Light stability as a function of concentration and further studies in metal stearate-stabiliser systems

The effect of concentration on the light stabilising efficiency of three metal chelates in polypropylene film has been examined. Both the calcium and nickel complexes of bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate (Irganox 1425 and Irgastab 2002, respectively) exhibit the same behaviour and have a limiting concentration above which no significant further photo-protection occurs. However, in the case of the nickel complex of 2,2′-thiobis(4-tert-octyl-phenolato) n-butylamine (Cyasorb UV 1084), there is a linear relationship between light stability and concentration up to 0·1% w/w of additive. Deviations from this linearity appear at higher concentration levels. The results confirm earlier conclusions that the photo-oxidation products of the first two chelates are photo-active, whereas those of the latter are themselves photo-stabilisers.Further studies on the effects of metal stearates on the stabilising action of the two nickel complexes have been carried out. In the case of Cyasorb UV 1084, synergism was observed with strontium stearate whereas antagonism was present with all the other stearates, their order of stability being Zn > Na > Mg > Co. On the other hand, all the stearates were antagonistic with Irgastab 2002, their order of stability being Na > Co ≈ Zn > Sr > Mg. The effects are accounted for on the basis of metal exchange, supporting our earlier findings.     

Synthesis, characterization and thermal degradation of functional benzoxazine monomers and polymers containing phenylphosphine oxide

Three phosphorus-containing bisphenol compounds, bis(4-hydroxyphenyl)phenylphosphine oxide (BHPPO), bis(4-hydroxyphenoxyphenyl)phenylphosphine oxide (BPPPO), and bis(4-hydroxyphenoxy)phenylphosphine oxide (BPHPPO) have been synthesized as starting materials for the synthesis of benzoxazine monomers. Benzoxazine monomers containing phenylphosphine oxide have been prepared and subsequently characterized by FT-IR and ¹H NMR. The monomers are thermally initiated and polymerized via ring-opening polymerization. Thermogravimetric analysis indicates that phosphorylation can have a profound effect on increasing char yield and on thermal degradation temperatures.     

Lower Rim Substituted p-tert-Butyl Calix[4]arenes (V). Synthesis of New 5,11,17,22-tetrakis-p-tert-Butyl-25,27-bis(methoxy)- 26,28-bis(dialkoxyphosphorylmethoxy)calix[4]arenes and Cation Complexation Studies in Ion-Selective Membrane Electrodes

The synthesis and characterization of the lower rim bis-phosphorylatedtetrakis-p-tert-butyl-25,27-bis(methoxy)calix[4]arenas(compounds 2–4) is presented. The studied compounds were examined as ionophores in ion-selective membrane electrodes, showing selectivity for rubidium, potassium, and for the large and flat guanidinium cations (G⁺). The correlation wasstudied between the stereochemical structure of the ligands andpotentiometrically determined ion-selectivity. Complex formationconstants in the PVC/BEHS (bis(ethyl)hexyl sebacate) membranes weredetermined. The crystal and molecular structures of compound 4 have been determined by single crystal X-ray diffraction study.     

Photo-stabilization of styrene-butadiene copolymer: The effect of 2,2′-thiodiethylbis-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate] on the photo-sensitized oxidation of styrene-butadiene copolymer

The effect of 2,2′-thiodiethylbis-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] (Irganox 1035) on the 9-methylanthracene sensitized photo-oxidation of styrene-butadiene copolymer (SBR) has been examined. It was found that the photo-oxidation of SBR is considerably inhibited by the Irganox. Irganox was found to be able to quench singlet oxygen as well as to scavenge alkoxyl radicals.     

An efficient one-pot three-step domino synthesis of substituted bis(pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidin-4(3H)-ones)

A convenient and efficient one-pot three-step domino approach to bis(pyrazinothienopyrimidinones) from ethyl 3-(triphenylphosphoranylideneamino)-thieno[2,3-b]pyrazine-6-carboxylate 1 has been developed. In this method, treatment of phosphazene 1 with a mixture of isocyanates, nitrogen, sulfur, and oxygen bis(nucleophiles) and K₂CO₃ in refluxing THF regioselectively furnishes the corresponding bis(pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidin-4(3H)-ones) in satisfactory to good yields. This methodology is highly versatile and efficient for the generation of these functionalized bis(triheterocyclic) compounds that are not readily available by other synthetic methods.