Oxidation of olefins with alkanesulfoperacids

Alkanesulfonic peracids RSO₄H effectively oxidize olefins to the corresponding epoxides. The kinetics and mechanism of this reaction are studied. It was shown that both the monomer and dimer form of the peracid act as oxidizing agents. The dependence of the weight constant of the reaction of monomer RSO₄H with substituted acyclic olefins on the structure of the latter is described by the Taft equation. A linear correlation is established between log k₂ and the inductive constants of the substituents on the oxygen atom in the peracid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 333–337, February, 1991.     

Pseudoelementverbindungen. VIII. [1]. Zum Komplexbildungsverhalten von potentiell ambidenten Aryl-cyanamidosulfonat-Liganden

Pseudoelement Compounds. VIII. [1]. On the Coordination Behaviour of Potential Ambidentate Aryl-cyanamidosulfonate Ligands Aryl-cyanamidosulfonates form with metal(II) ions (Co, Ni, Cu, Zn, Cd, Hg, Pd, Pt) complexes of the types MX₂, [MX₂L₂], [MX₂L₄] and [MX₄]^2?. The ionic, potentially ambidentate ligand [RSO₂NCN]^? is monodentately coordinated via the terminal nitrogen atom and bidentately in a bridging function through the nitrile group end-on (equatorial) and one of the two sulfonyl oxygen atoms (axial). The new compounds are characterized by means of ir and uv-vis spectroscopy. In the case of [Ni(NCNSO₂C₆H₄Me-4)₂(py)₄] the molecular and crystal structure was determined.     

The kinetics of acid-catalyzed decomposition of decanepersulfonic acid

The kinetics of thermal decomposition of decanepersulfonic acid (RSO₂OOH, R=C₁₀H₂₁) in CCl₄ in the presence of cyclohexanesulfonic and trifluoroacetic acids at 323–343 K was studied. The reaction has an autocatalytic character. The kinetics of consumption of the persulfonic acid is described by the equation-d[RSO₂OOH]/dt=k ₁[RSO₂OOH]+k ₂[RSO₂OOH]·[HX]. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 202–203, January, 1999.     

Analysis of sodium alkylsulphonates using filament heated in-beam electron impact mass spectrometry

Summary By means of the filament heated in-beam method at 280–450° C, the series of sodium alkylsulphonates (RSO₃Na, where R=C₂H₅ to n-C₁₂H₂₅) give very simple mass spectra: Na⁺, [RSO₃Na₂]⁺, which is the base peak except for R=n-C₄H₉, [(RSO₃)₂Na₃]⁺ and, in most cases, [(RSO₃)₃Na₄]⁺. Fragmentations other than these three or four peaks are observed only in the case of n-heptylsulphonate. The proposed method of analysis for simple alkylsulphonic acids is applicable to ordinary electron-impact mass spectrometers.

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Analyse von Natrium-alkylsulfonaten durch Elektronenstoß-Massenspektrometrie mit Probenerhitzung im Elektronenstrahl

Zusammenfassung Mit Hilfe dieser Methode (280–450° C) erhält man für Natriumalkylsulfonate (RSO₃Na mit R=C₂H₅ bis n-C₁₂H₂₅) sehr einfache Massenspektren: Na⁺, [RSO₃Na₂]⁺ (Basispeak mit Ausnahme von R=n-C₄H₉), [(RSO₃)₂Na₃]⁺ und in den meisten Fällen [(RSO₃)₃Na₄]⁺. Andere Fragmentierungen als diese 3 oder 4 Peaks wurden nur bei n-Heptylsulfonat beobachtet. Dieses Verfahren zur Analyse einfacher Alkylsulfonsäuren ist für übliche Elektronenstoß-Massenspektrometer verwendbar.

     

Layered coordination polymer of silver methanesulfonate with 2,3,5,6-tetramethylpyrazine

The complex [Ag₂(Me₄-Pyz)(CH₃SO₃)₂]·2H₂O is synthesized, and its structure is determined. The crystals are monoclinic, space group P2₁ /n,a = 11.821(1), b = 4.906(1), c = 15.782(1) Å,β = 94.34(1) °, V = 912.5(2) ų, ρ(calcd) = 2.104 g/cm³, Z = 2. The Ag⁺ ion is coordinated at the vertices of the distorted tetrahedron by the nitrogen atom of tetramethylpyrazine and three oxygen atoms of two methanesulfonate ions (Ag(1)-N(1) 2.283(2), Ag (1)-O(RSO ₃ ^? )2.386(3)-2.451(2) Å, angles at the Ag atom 86.8(1)°–129.1(1)°). The structure contains layers of sulfonate-silver chains and tetramethylpyrazine molecules extended along the direction [101].     

The synthesis of metal–organic framework Al‐MIL‐53‐derived Brønsted acid catalyst and its application in the Mannich reaction

A metal–organic framework Al‐MIL‐53‐NH₂‐derived Brønsted acid catalyst (Al‐MIL‐53‐RSO₃H) has been synthesized employing a post‐synthetic modification strategy under mild conditions. The Al‐MIL‐53‐RSO₃H catalyst was successfully utilized in the nitro‐Mannich reaction taking advantage of its strong Brønsted acidity. Good to excellent yields of Mannich adducts were achieved for a variety of acylimine substrates in the presence of 0.1 mol% Al‐MIL‐53‐RSO₃H. Furthermore, the Al‐MIL‐53‐RSO₃H catalyst can be recycled five times without decreasing the yield and selectivity of Mannich adducts.     

Mass spectra of heterocyclic compounds. II-Hexahydro-1,3,5,-triazines

The twelve tri-N-sulphonylhexahydro-1,3,5-triazines (R = alkyl or aryl) exhibit a common fragmentation pattern; most of the fragments are directly or indirectly generated from the [M ? RSO₂]⁺ ion. Tri-N-Benzylsulphonylhexahydro-1,3,5-triazine (R = PhCH₂) departs from the others mainly because the key ion [M ? RSO₂]⁺ suffers a skeletal rearrangement with loss of SO₂. The rationalizations presented are supported by metastable evidence, accurate mass measurements and deuterium labelling.     

Die Kristallstruktur des Trimethylzinn-methansulfinats, (CH3)3Sn02SCH3

The Crystal Structure of Trimethyltin Methanesulfinate, (CH₃)₃SnO₂SCH₃ Trimethyltin methanesulfinate, (CH₃)₃SnO₂SCH₃ crystallizes orthorhombie in the space group A2₁22. The lattice constants are: a = 7.98 ± 0.01, b = 12.59 ± 0.02 and c = 17.83 ± 0.02 Å Within the crystal structure the Sn atoms are linked together via bridging RSO₂ groups to form a helical chain along [l00]. Each Sn atom is surrounded by three C and two 0 atoms in a trigonal bipyramidal arrangement. The Sn? C distances are in the range from 2.09 to 2.18 Å the Sn? 0 distance amounts to 2.23 Å.     

Reaction of α-polynitroalkyl sulfones with nucleophilic and electrophilic reagents

Conclusions Under mild conditions -polynitroalkyl sulfones with the general formula RSO₂C(NO₂)₂R are split at the C-SO₂ bond under the action of both nucleophilic (alcohols, water, and bases) and electrophilic (the halogens, SO)₂Cl₂, BrONO₂, and HC1) reagents to form the corresponding polynitroalkane and sulfonic acid derivatives. The attack of the nucleophiles is directed at the sulfur atom, and that of the electrophiles is directed at the -carbon atom bonded to the nitro groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 375–380, February, 1977.We thank G. V. Antoshina and E. S. Shpiro for recording and interpreting the x-ray photoelectron spectra.     

Pseudoelementverbindungen. IV. Modifizierung der Ionen Sulfit [SOY2]2−, Sulfat [SO4−nYn]2− und Sulfonat [RSO2Y]− durch Einführung der Pseudochalkogengruppen NCN und C(CN)2

Pseudoelement Compounds. IV. Modification of the Ions Sulfite [SO₂Y]^2?, Sulfate [SO_4?nY_n]^2?, and Sulfonate [RSO₂Y]^? by Introducing Pseudochalcogen Groups NCN and C(CN)₂ . Described is the synthesis of pseudochalcogen modified sulfites M₂[SOY₂], sulfates M₂[SO_4?nY_n] (Y = NCN), and arylsulfonates M[RSO₂Y] (Y = NCN, C(CN)₂). The ¹³C-NMR and IR spectra of the new compounds are discussed.     

Organofluorine sulfur-containing compounds

Polyfluorinated aryldifluoromethyl sulfides have been obtained by treatment of polyfluorinated 4-X-substituted thiophenols with chlorodifluoromethane in an alkaline medium. Reactions of difluoromethylpentafluorophenyl sulfide with H₂O₂, KMnO₄, and HNO₃, giving the corresponding sulfoxide and sulfone, were studied.     

Adsorbate-substrate interaction between chlorodifluoromethane and titanium dioxide: Infrared spectroscopy and density functional theory studies

Infrared spectra of chlorodifluoromethane (CHClF₂) adsorbed on titanium dioxide (TiO₂) at room temperature have been investigated for the first time. From the comparison between the adsorption characteristics and the gas-phase spectra it can be deduced that the molecule interacts with the surface Lewis acid site (Ti⁴⁺) mainly through the Cl atom even if also the adsorption with one F atom is also observed. Moreover, the spectra show the presence of H-bonds between the CH group and the surface Lewis basic site (OH⁻ or O²⁻). In order to obtain more information on the molecule orientation and the variation of the structural parameters, a DFT-B3LYP study has been carried out considering the anatase (1 0 1) surface and evaluating the adsorption energetics in terms of interaction, distortion and binding energies. The obtained geometries confirm that both the acid-base interactions through Cl or F atoms are possible and suggest the formation of one H-bond between the CH group of the molecule and the Lewis basic site of the surface. The calculated vibrational frequencies of the adsorbed molecule have been found to be in reasonable agreement with the experimental data.     

Polysulfonylamine. LVII. Zwei Silber(I)-di(organosulfonyl)-amide mit einer Silber-η2-Aryl- beziehungsweise einer Silber-Silber-Wechselwirkung: Kristallstrukturen von Silberdi(benzolsulfonyl)-amid-Wasser (1/0,5) und von wasserfreiem Silberdi(4-toluolsulfonyl)-amid

Polysulfonyl Amines. LVII. Two Silver(I) Di(organosulfonyl)-amides with Silver-η²-Aryl or Silver-Silver Interactions: Crystal Structures of Silver Di(benzenesulfonyl)amide-Water (1/0.5) and of Anhydrous Silver Di(4-toluenesulfonyl)-amide Crystals of [(PhSO₂)₂NAg(μ-H₂O)AgN(SO₂Ph)₂]_n ( 5 ) and [(4-Me? C₆H₄SO₂)₂NAgAgN(SO₂C₆H₄-4-Me)₂]_n ( 6 ) were obtained from aqueous solutions. The crystallographic data are for 5 (at ?95°C): monoclinic, space group C2/c, a = 2 743.8(5), b = 600.49(12), c = 1 664.5(3) pm, β = 101.143(15)°, V = 2.6908 nm³, Z = 8, D_x = 2.040 Mg m^?3; for 6 (at ?130°C): monoclinic, space group P2₁/n, a = 1 099.8(5), b = 563.7(3), c = 2 487.7(13) pm, β = 99.68(4)°, V = 1.5203 nm³, Z = 4, D_x = 1.888 Mg m^?3. In both crystals, the silver atom has a fivefold coordination. The structure of 5 displays [(RSO₂)₂N? Ag(μ-H₂O)Ag′? N(SO₂R)₂] units with Ag? N 226.9 pm, Ag? O 236.7 pm and Ag? O? Ag′ 95.3°; the water oxygen lies on a crystallographic twofold axis. These units are extended to two fused six-membered rings by intramolecular dative bonds (S)O → Ag′ and S(O)′ → Ag (249.3 pm). One phenyl group from each (PhSO₂)₂N moiety is η²-coordinated with its p-C and one m-C atom to a silver atom of a neighbouring bicyclic unit related by a glide plane to form infinite parallel strands (p-C? Ag 252.2, m-C? Ag 263.9 pm). The strands are interconnected into parallel layers through hydrogen bonds between H₂O and sulfonyl oxygens [O …? O(S) 276.1 pm]. These layers consist of a hydrophilic inner region containing metal ions, N(SO₂)₂ fragments and water molecules, and hydrophobic surfaces formed by phenyl groups. The structure of 6 features centrosymmetric [(RSO₂)₂N? Ag? Ag′? N(SO₂R)₂] units with two intramolecular dative bonds (S)O → Ag′ and (S)O′ → Ag (Ag? Ag′ 295.4, Ag? N 226.0, Ag? O 229.4 pm). These bi-pentacyclic units are associated by translation parallel to y into infinite strands by two dative (S)O → Ag bonds per silver atom (Ag? O 243.2 and 253.3 pm).     

Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity of Atomic Nitrogen

To investigate the intrinsic reactivity of atomic nitrogen, which had previously been accomplished only by examining its decay in the gas phase using special equipment, a nitrogen atom was inserted into a series of molecule-encapsulating C₆₀ and C₇₀ fullerenes. Among the studied endofullerenes, H₂@C₇₀ was able to encapsulate an additional nitrogen atom within the fullerene cage under radiofrequency plasma conditions. The product was analyzed by ESR spectroscopy and mass spectrometry in solution, which revealed that the nitrogen atom with a quartet ground state does not react but weakly interact with the H₂ molecule, thus demonstrating the utility of such fullerenes as “nanoflasks”.     

Mass spectra of sulfinamide derivatives and identification of their thermal decomposition products

The mass spectra of 30 sulfinamide derivatives (RSONHR', R' alkyl or p-XC₆H₄) are reported. Most of the spectra had peaks attributable to thermal decomposition products. For some compounds these were identified by pyrolysis under similar conditions to be: RSO₂NHR', RSO₂SR, RSSR and NH₂R' (in all kinds of sulfinyl amides); RSNHR' (in the case of arylsulfinyl arylamides); RSO₂C₆H₄NH₂, RSOC₆H₄NH₂ and RSC₆H₄NH₂ (in the case of arylsulfinyl arylamides of the type of X = H) The mass spectra of the three thermally stable compounds showed that there are several kinds of common fragment ions. The mass spectra of the thermally labile compounds had two groups of ions; (i) characteristic fragment ions of the intact molecules and (ii) the molecular ions of the thermal decomposition products. It was concluded that the sulfinamides give the following ions after electron impact: [M]⁺, [M ? R]⁺, [M ? R + H]⁺, [M ? SO]⁺, [RS]⁺, [NHR']⁺, [NHR' + H]⁺, [RSO]⁺, [RSO + H]⁺, [R]⁺, [R + H]⁺, [R']⁺ and [M ? OH]⁺, and that the thermal decomposition products give the following ions: [RSO₂SR]⁺, [RSSR]⁺, [M ? O]⁺, [M + O]⁺ and [RSOC₆H₄NH₂]⁺.     

Separation of Free Amiimo Acids on Reverse Stationary Phases Using an Alkyl Sulfonate Salt as a Mobile Phase Additive

Abstract

Alkylsulfonate (RSO₃ ^?) salts were evaluated as mobile phase additives for the separation of free amino acids on reverse stationary phases using an acidic mobile phase where the amino acids are cations. The enhanced amino acid retention is the result of two major interactions, one being retention of the RSO₃ ^? salt on the stationary phase and the other an ion exchange selectivity between the amino acid analyte cation and the RSO₃ ^? countercation, or other countercations in the mobile phase. Major mobile phase variables are: type and concentration of RSO₃ ^? salt (the studies focused on C₈SO₃ ^? salts), presence of organic modifier, type of countercation present, and mobile phase pH and ionic strength. Alkyl modified silica and polystyrenedivinyl-benzene copolymeric reverse stationary phases were compared. A mobile phase gradient, increasing per cent organic modifier was shown to be best, is necessary for separating complex mixtures of polar and nonpolar or basic amino acids. The procedure is applicable to the identification and/or determination of amino acids in mixtures or in peptides after hydrolysis.     

Kinetics of oxidation of 2,2,4,5,5-pentamethyl-1-hydroxy-3-imidazoline-3-oxide by decanepersulfonic acid

The kinetics was studied of the oxidation of 2,2,4,5,5-pentamethyl-1-hydroxy-3-imidazoline-3-oxide by decanepersulfonic acid in a chloroform solution. The corresponding nitroxyl radical is quantitatively formed by the reaction 2=N-OH + RSO₄H 2=NO + RSO₃H + H₂O A mechanism of the reaction was proposed and the rate constant of the limiting stage of the process was determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1265–1268, June, 1990.     

含喹噁啉环高聚物金属络合物结构的X-射线光电子能谱XPS测定

<正> 本文报道聚[2,2′-(1,4-次苯基)-6,6′-氧双(3-苯基喹(口恶)啉)](简称PPQ)金属络合物的X-射线光电子能谱(XPS)研究,作为杂环高分子之一的PPQ与某些过渡金属(铑,铂)氯化物间生成的化合物具有很好的催化活性,因而探讨这种杂环高分子与金属氯化物间的直接键合作用及其结构对探明杂环高分子金属络合物的催化机理起重要作用。     

On the Search of Metallated Sulfonamides: Synthesis and X‐ray Characterization of the New Sulfathiazolato Nickel(II)‐Chelate Complex [Ni(STZ)2(Py)2]·2Py (STZ = Sulfathiazolato Anion; Sulfathiazole = N1‐2‐thiazolyl‐sulfanilamide; Py = Pyridine)

Sulfathiazole (HSTZ) reacts with triethylamine and Ni(CH₃COO)₂·4H₂O in methanol and further with pyridine to give the sulfathiazolato complex [Ni(STZ)₂(Py)₂]·2Py. In the new chelate complex the deprotonated sulfonamidic nitrogen atom does not take part in the coordination process, apparently retaining the negative charge. Two (STZ)^? moieties are symmetrically bonded to the Ni²⁺ ion through a thiazolyl nitrogen atom and an oxygen atom of the S(O)₂ group. Two pyridine molecules accomplish the fairly distorted octahedral coordination at the metal centre.     

Synthesis and Theoretical Study of Vanadium Oxotrichloride Complex of Hexachlorotriphosphazene and Ab Initio Investigations of Some Simple Cyclic Triphosphazenes

N₃P₃Cl₆·VOCl₃ results from the reaction between vanadium oxotrichloride and hexachlorotriphosphazene in dichloroethane. Vanadium oxotrichloride coordination with nitrogen atom in the phosphonitrile ring was detected from the IR spectrum of the product. Quantum-chemistry calculations for (NPX₂)₃ (X = H, F, Cl, NH₂) were carried out as well. A comparative study of some basic characteristics of the simple cyclotriphosphazenes' electronic structures was carried out. Quantum-chemistry calculations also were done for the complex of hexachlorophosphazene with vanadium oxotrichloride. It is shown that the nitrogen atom in phosphazenes plays an essential role for donor-acceptor interactions and is the most preferable atom for binding with a vanadium atom.