- First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase
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Condensed phase access to the unprecedented tetrahedral cations [EP3]+ (E = S, Se, Te) was achieved through the reaction of ECl3[WCA] with white phosphorus ([WCA]- = [Al(ORF)4]- and [F(Al(ORF)3)2]-; -RF = -C(CF3)3). Previously, [EP3]+ was only known from gas phase MS investigations. By contrast, the reaction of ECl3[A] with the known P33- synthon Na[Nb(ODipp)3(P3)] (enabling AsP3 synthesis), led to formation of P4. The cations [EP3]+ were characterized by multinuclear NMR spectroscopy in combination with high-level quantum chemical calculations. Their bonding situation is described with several approaches including Atoms in Molecules and Natural Bond Orbital analysis. The first series of well-soluble salts ECl3[WCA] was synthesized and fully characterized as starting materials for the studies on this elusive class of [EP3]+ cations. Yet, with high [ECl3]+ fluoride ion affinity values between 775 (S), 803 (Se) and 844 (Te) kJ mol-1, well exceeding typical phosphenium ions, these well-soluble ECl3[WCA] salts could be relevant in view of the renewed interest in strong (also cationic) Lewis acids.
- Weis, Philippe,R?hner, David Christopher,Prediger, Richard,Butschke, Burkhard,Scherer, Harald,Weber, Stefan,Krossing, Ingo
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p. 10779 - 10788
(2019/12/03)
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- Reactions of P(III) chlorides with aldehydes: I. Synthesis of primary intermediates of the reactions of aliphatic aldehydes with P(III) chlorides possessing electrophilic properties
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An approach to investigation of reactions of electrophilic P(III) chlorides with aliphatic aldehydes is developed. Its essence is the removal of HCl impurity from chloride and catalytic blocking of electrophilic center of the carbonyl group. For these pur
- Gazizov,Khairullin,Karimova
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p. 2281 - 2292
(2014/03/21)
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- Silicate compounds for DNA purification
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The present invention relates to a silicon-containing material which exhibits sufficient hydrophilicity and sufficient electropositivity to bind DNA from a suspension containing DNA and permit elution of the DNA from the material. Generally, the hydrophilic and electropositive characteristics are expressed at the surface of the silicon-containing material. Preferred silicon-containing materials of the present invention include boron silicate, aluminum silicate, phosphosilicate, silica carbonyl, silica sulfonyl and silica phosphonyl. The silicon-containing materials of the present invention are particularly useful in processes for purification of DNA from other cellular components. In these processes, a suspension of cellular components is placed in contact with the silicon-containing material, the silicon-containing material is washed to remove all cellular components other than DNA which are bound to the material, and the bound DNA is eluted from the material. Several of the silicon-containing materials are capable of binding and eluting DNA using only water.
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- UNTERSCHIEDLICHES VERHALTEN VON AROMATISCHEN PHOSPHITEN GEGENUEBER ACYLSULFENYLCHLORIDEN
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The acylsulfenyl chlorides 1 or 2 react with acyclic and cyclic aromatic phosphites.The acyclic derivative 3 gives the corresponding thiophosphate 4 and the cyclic derivatives 5 give the corresponding phosphates 6.The different behaviour is discussed. Key words: Acylsulfenyl chlorides; aromatic phosphites; oxidation of P(III) compounds.
- Gloede, J.,Lutze, G.
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p. 265 - 270
(2007/10/02)
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- Process for obtaining bis(2,4-di-tert-butylphenyl) halophosphites
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The invention relates to a process for obtaining phosphorus acid-bis(2,4-di-tert-butylphenyl) ester halides in which a phosphorus acid-2,4-di-tert-butylphenyl ester dihalide is heated in the presence of a catalyst containing nitrogen or phosphorus, or both, to 130° C. to 280° C. and the phosphorus trihalide produced by disproportionation is removed from the reaction mixture.
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- Reactivity of Sulphuryl Chloride in Acetonitrile with the Elements
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Sulphuryl chloride in MeCN reacts with all but the most refractory elements to give mainly solvated chlorides at or below 300 K in contrast with SO2Cl2 alone which requires at least twice this temperature.There is evidence for an ionic mechanism based on analogy, thermochemistry, transport measurements and additive effects.The instability of these solutions leading to polymerization, together with its inhibition, is described.Sulphur dioxide formed in reactions seldom plays a reductive role apart from influencing formation of the mixed-valence Tl4Cl6.Semiquantitative kinetic measurements in different solvents emphasize the uniqueness of MeCN.For most elements attack is diffusion controlled across surface films giving a parabolic dependence on time which can be linearized if film growth is prevented by changing the solvent mix.The varied nature of these surface films vitiates any simple relation between rate and periodicity.Some applications are indicated.
- Woolf, Alfred A.
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p. 3325 - 3330
(2007/10/02)
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- 2-Methyl-1-nitrilo-2-methyl -1-hydroxylamino-3-(methoxyphenyl) propane, organoleptic uses thereof and processes for preparing same
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Described are 2-methyl-1-nitrilo- or 2-methyl-1-hydroxylamino-3-(methoxyphenyl) propanes defined according to the generic structure: STR1 wherein R1 is selected from the group consisting of: (i) cyanide having the structure: STR2 (ii) hydroxylaminomethyl having the structure: uses thereof in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles including but not limited to bleach compositions, solid or liquid anionic, cationic, nonionic or zwitterionic detergents, perfumed polymers, fabric softener compositions, fabric softener articles, cosmetic powders and hair preparations. Also described are processes for preparing such 2-methyl-1-nitrillo- or 2-methyl-1-hydroxylamino-3-(methoxyphenyl) propanes by means of reacting a methoxy benzyl halide with ethyl cyanide in the presence of a basic catalyst such as sodamide.
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- Chemiluminescent reactions of group IV A atoms with PCl5 and SnCl4
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Earlier work to chemiluminescent (CL) reaction of group IV A atoms with halogens has been extended to two chlorine-rich molecules PCl5 and SnCl4.The CL products in these reactions were found to be group IV A dihalides formed in a one step mechanism instead of the two step mechanism proposed in the study of the reactions involving Br2, I2, and ICl.For PCl5. the CL products were found to be group IV A dichlorides, while for SnCl4, the CL products are believed to be SnCl2 for all three atoms.The overall absolute cross sections for the reactions have been estimated, as well as the relative cross sections as functions of collisional energy.The observation of different collisional energy dependence for the reactions of PCl5 and SnCl4, along with other evidence, suggests that two different mechanisms produce the CL products in the two groups of reactions.
- Wang, J.H.,Cheong, B.S.,Fang, C.C.,Parson, J.M.
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p. 7830 - 7835
(2007/10/02)
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- Preparation and spectroscopic characterization of difluorophosphorane, PH3F2. 31P NMR spectrum of protonated diphosphine, P2H5+
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The preparation of difluorophosphorane, PH3F2, from the reaction of diphosphine and hydrogen fluoride is reinvestigated; it has been characterized by multinuclear (1H, 19F, 31P) NMR spectroscopy. Complete infrared and Raman low-temperature spectra of difluorophosphorane are reported. It reacts with alkali-metal fluorides to give phosphine and hexafluorophosphates(V). On the basis of 31P NMR spectroscopic results, a reaction mechanism for the formation of PH3F2 is proposed. The byproducts of the reaction were PH2F3, (PH)n, and P2H5+; the last was observed for the first time. In carbon disulfide solution, diphosphine neither reacts with hydrogen halides to yield protonated diphosphine nor interacts with hydrogen fluoride to form difluorophosphorane.
- Minkwitz, Rolf,Liedtke, Andreas
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p. 4238 - 4242
(2008/10/08)
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- Process for making chlorophosphines and thiophosphinic acid chlorides, and 9-chloro-9-thioxo-9-phosphabicyclononanes
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Chlorophosphines or thiophosphinic acid chlorides of the general formulae RPCl2, R2 PCl or R2 P(=S)Cl are made from feed materials selected from hydrogen-functional primary or secondary phosphines or secondary phosphine sulfides, where R stands for identical or different, linear or branched, substituted or unsubstituted alkyl radicals having from 1-16 carbon atoms, aryl radicals, aralkyl radicals or alkylaryl radicals having from 6-9 carbon atoms or cycloalkyl radicals having from 5-10 carbon atoms. To this end, the feed materials are reacted with phosphorus pentachloride, or with chlorine gas in the presence of phosphorus trichloride at temperatures within the range -78° to +145° C. It is possible for two radicals R to be linked together by one or two substituted or unsubstituted hydrocarbon chains having from 1-4 carbon atoms.
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- BRANCHED-CHAIN REACTION OF CHLORINE WITH PHOSPHINE.
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A new, branched-chain process has been found, the chlorination of phosphine with molecular chlorine. Two, qualitatively different, reaction regimes are described which depend on the pressure of the reaction mixture. A mechanism of chain initiation is proposed which involves the formation of the complex PH//3Cl//2.
- Azatyan,Gagarin,Zakhar'in,Kalkanov,Kolbanovskii
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p. 191 - 194
(2008/10/08)
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- Reactions of Tetraphosphorus Trisulphide with Organic Disulphides under Ultraviolet Irradiation, and with Sulphuryl Chloride
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P4S3 under glass-filtered u.v. irradiation is rapidly cleaved by alkyl and aryl disulphides to give tetrathiophosphate esters, SP(SR)3, and trithiophosphite esters, P(SR)3 (R = Me or Ph), in quantitative yield, as measured in the product mixture by 31P and 1H n.m.r. spectroscopy.No sulphurisation of P4S3 was found.In a competition reaction, MeSSMe and PhSSPh reacted to a similar extent with P4S3 to give all eight possible products SxP(SPh)n(SMe)(3-n) (x = O or 1, n = 0-3) in relative quantities within each oxidation state approximating to a statistical distribution of ligands, but there was more MeS substitution of the phosphorus (V) produts and more PhS substitution of the phosphorus(III) products.Reaction of MeSSPh with P4S3 gave similar results.Redistribution of ligands took place when a mixture of P(SMe)3 and P(SPh)3 was photolysed, and photolysis of a mixture of P(SMe)3 and MeSSPh caused the PhS group to be distributed between the trithiophosphite and disulphide sites.P(SMe)3 and P(SPh)3 were not sulphurised by MeSSMe and PhSSPh respectively, but P(SMe)3 was sulphurised to SP(SMe)3 to a small extent by MeSSPh.P4S3 is similarly cleaved by sulphuryl chloride, but under thermal conditions, to give SPCl3 and PCl3, with no evidence for intermediates.
- Musa, Faleh H.,Tattershall, Bruce W.
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p. 1517 - 1520
(2007/10/02)
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- Structure and Fluxionality in the PF6-n(CN)n- and PF3Cl3-n(CN)n- Series
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Several new ions in the series PF6-n(CN)n- and PF3Cl3-n(CN)n- have been prepared, and identified by n.m.r. spectroscopy; some species with three or more fluorine atoms present are fluxional at 307.2 K.
- Dillon, Keith B.,Platt, Andrew W. G.
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p. 1089 - 1090
(2007/10/02)
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- Cyano and Thiocyanato-derivatives of the Hexachlorophosphate Ion (PCl6(1-))
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The preparation and identification in solution of several new cyano- and thiocyanato-derivatives of the hexachlorophosphate (PCl6(1-)) ion are described.The cyano-complexes (1-) (n = 1-3) and the hexathiocyanatophosphate ion P(NCS)6(1-) have been isolated as tetra-n-alkylammonium salts and further characterised by elemental analysis, (31)P n.m.r., and (in some cases) vibrational spectroscopy.The mer isomer of the (1-) ion has been obtained pure and the fac isomer in a less pure state (ca. 3:1 fac:mer) by different preparative routes.Isomeric configurations in the chlorothiocyanatophosphate series (1-) have been assigned on the basis of the pairwise interaction method.
- Dillon, Keith B.,Platt, Andrew W. G.
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p. 1199 - 1204
(2007/10/02)
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- Terpenophenols
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New terpenophenols of the general formula: STR1 wherein R is a 2-isobornyl, 5-camphyl or 2-norbornyl group of exo or endo configuration and in the ortho, meta or para position with respect to the OH group; R1, R2 may each be a hydrogen atom or halogen atom (Cl, Br, F, I) or a lower alkyl or lower alkoxy radical having a straight or branched chain of 1 to 4 carbon atoms or a nitro or cyano group.
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- 1-Aminoalkane-1,1-diphosphonic acids and their salts
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A process for the production of 1-aminoalkane-1,1-diphosphonates of the formula SPC1 Wherein R1 is a member selected from the group consisting of hydrogen, lower alkyl and phenyl, R2 and R 3 are members selected from the group consisting of hydrogen, alkyl having 1 to 22 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, phenyl, alkylphenyl having 7 to 18 carbon atoms, phenylalkyl having 7 to 18 carbon atoms and together with the nitrogen atom, piperidino, pyrrolidino and morpholino, and X is a member selected from the group consisting of hydrogen, alkali metal, ammonium, pyridinium, guanidinium and mono-, di-, and tri-lower-alkanol-ammonium with the proviso that at least one of R1, R2 and R3 is other than hydrogen, which consists essentially in reacting a phosphorus trihalide selected from the group consisting of phosphosus trichloride and phosphorus tribromide with a monocarboxylic acid amide of the formula SPC2wherein the molecular weight of said carboxylic acid amide is over 46 and R1, R2 and R 3 have the above assigned meanings, at a temperature of from 0° to 75°C, subjecting the resultant reaction product to hydrolysis, and recovering said 1-aminoalkane-1,1-diphosphonates. The 1-aminoalkane-1,1-diphosphonates, some of which are novel, are capable of forming complexes with heavy metals.
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- Process for preparing alkane bis-dihalophosphines
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Alkane bis-dihalophosphines are prepared by reacting an olefin with a trivalent phosphorus compound having three halogens attached thereto, such as phosphorus trichloride, in the presence of elemental phosphorus under at least autogenous pressure at a temperature of from 150°C. to 350°C. The compounds obtained are useful as intermediates in preparing organophosphorus compounds which can be used as insecticides, fungicides, pharmaceuticals, flame retardant compounds, and in forming metal complexes which are catalyst activators.
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- Reactivity of transition metal fluorides. II. Uranium hexafluoride
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Reactions have been studied between uranium hexafluoride and a series of lower fluorides of other elements. The study has also included reaction with a wide range of covalent chlorides. The reactivity of uranium hexafluoride is compared with that of the higher fluorides of d-transition elements, chromium, molybdenum, and tungsten, and considered in the light of uranium as an f-transition element.
- O'Donnell,Stewart,Wilson
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p. 1438 - 1441
(2008/10/08)
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