Showing papers on "Halogen published in 1969"

Nuclear magnetic shielding of hydrated alkali and halide ions in aqueous solution

Abstract: Various methods for the determination of the paramagnetic term of the shielding constant of alkali and halide ions in dilute aqueous solution are discussed. Values of the chemical shift of the hydrated ions, σp Maq+ and σp Xaq− , are obtained from solvent isotope chemical shifts of halide ions; spin relaxation rates of quadrupolar nuclei in dilute aqueous solution and from the concentration dependence of the chemical shift and relaxation rates of alkali and halogen nuclei in aqueous solutions of alkali halides.

Catalytic synthesis of organic halogen compounds from an ethylenically unsaturated compound and a halogenated organic compound

Abstract: Method for forming a chemical adduct of an ethylenically unsaturated compound with a halogenated organic compound having on a single carbon atom thereof at least two halogen atoms at least one of which is chlorine, bromine or iodine, characterized by employing a catalyst of which the essential members are copper and an amine selected from piperidine, substituted piperidines, cyclohexylamines and secondary amines on which the hydrocarbyl substituents are allyl, benzyl or lower alkyl radicals.

Synthetic Photochromic Sodalite

Abstract: Synthetic photochromic sodalite was prepared (1) by solid-state reaction, (2) from zeolite X-SO2 or zeolite X-H2S, and (3) hydrothermally; the preparations are compared and discussed. X-ray diffraction, ultraviolet and visible light absorption (transmission and reflection), and ESR data served to follow the reactions and characterize the products. The content of sulfur and chlorine and the S: C1 ratio affect the depth of color and the bleaching rate. The partial substitution of other halogens for C1 may speed up or slow down the coloring rate as a function of electronegativity. Fluorine may shift the visible absorption maximum from 5300 to 5100 A. Stoichiometry and ESR data indicate that the photochromism is effected by the transfer of an electron between sulfur as S2= and a C1 vacancy between four sodium atoms.

Purine-ribofuranoside-3',5'-cyclophosphates and process for their preparation

Abstract: NOVEL PURINE-RIBOFURANOAIDE-3'',5''-CYCLOPHOSPHATE COMPOUNDS OF THE FORMULA: 2-B,7-(2,3-(-CH2-O-P(=O)(-OH)-O-),4-Y-FURAN-5-YL),6-Z- PURINE WHEREIN B IS A HYDROGEN ATOM OR A HYDROXYXYL OR AMINO GROUP; Z IS A HALOGEN ATOM, AN ETHER GROUP OR A MONOOR DISUBSTITUTED AMINO GROUP WHEN X IS A HYDROGEN ATOM AND OTHERWISE Z IS A HYDROGEN ATOM, A HYDROXYL GROUP OR AN UNSUBSTITUTED AMINO GROUP, Y IS A HYDROXYL GROUP OR, WHEN X IS OTHER THAN A HYDROGEN ATOM, Y IS A HYDROGEN ATOM AND X IS A HYDROGEN OR HALOGEN ATOM, A HYDROXYL GROUP, AN ETHER GROUP, A SULPHYDRYL GROUP, A THIOETHER GROUP OR AN UNSUBSTITUTED OR SUBSTITUTED AMINO GROUP; AND THE SALTS THEREOF, ARE PROVIDED; THESE COMPOUNDS CAN BE PREPARED BY REACTING THE CORRESPONDING CYCLOPHOSPHATE WHEREIN Y AND Z IN THE ABOVE FORMULA ARE HYDROXY, AND X IS HYDROGEN, WITH (A) PHOSPHORUS OXYHALIDE AFTER ACYLATION OR (B) MOLECULAR HALOGEN IN ALKALINE MEDIUM, TO FORM THE CORRESPONDING (A)6-HALO OR (B) 8-HALO COMPOUND, AND THE 6- OR 8-HALO COMPOUND THEREBY OBTAINED IS CONVERTED, IF NECESSARY, INTO THE CORRESPONDING DESIRED COMPOUND BY, E.G., REACTING THE HALO COMPOUND WITH AN ALCOHOL OR ALCOHOLATE TO GIVE THE CORRESPONDING ETHER; OR WITH AMMONIA OR AN AMINE TO GIVE THE CORRESPONDING AMINO COMPOUND; OR WITH HYDRAZINE TO GIVE THE CORRESPONDING HYDRAZIDE; OR WITH THIOUREA OR AN ALKYL SULFIDE TO GIVE THE CORRESPONDING SULPHHYDRYL COMPOUND, WHICH CAN IN TURN BE CONVERTED TO THE THIOETHER COMPOUNDS.

Nuclear quadrupole resonance of charge-transfer complexes. II. The aminehalogen complexes

Abstract: Nuclear quadrupole resonance frequencies have been measured for some of the halogen nuclei in a number of crystalline charge-transfer complexes of amines with bromide, iodine, iodine monobromide, and iodine monochloride. From these measurements it has been possible to calculate approximate charge distributions for the bromine, iodine monobromide, and iodine monochloride complexes of 3,5-di-bromopyridine. The results correlate well with a three-centre delocalized LCAO-MO bonding theory. The correlation of this MO description with Mulliken's charge-transfer bonding scheme for n-σ complexes is discussed. This approach indicates the importance of considering an ?ionic? structure (which does not involve transfer of charge from the donor to the acceptor) in the electronic ground state of these complexes.

Process for the preparation of 3-isothiazolones and 3-hydroxyisothiazoles

Abstract: -S-CH(-Z)-CH(-X)-CO-NH-Y X AND Z ARE INDIVIDUALLY HYDROGEN OR A LOWER ALKYL GROUP, AND Y IS AS DEFINED ABOVE, AND WHEREIN THE HALOGENATING AGENT IS PRESENT TO THE EXTENT OF AT LEAST TWO MOLE EQUIVALENTS WHEN Q IS HYDROGEN OR TO THE EXTENT OF AT LEAST THREE MOLE EQUIVALENTS WHEN Q IS -S-CH(-Z)-CH(-X)-CO-NH-Y WHEREIN Q IS HYDROGEN OR Q-S-CH(-Z)-CH(-X)-CO-NH-Y R AND R1 MAY BE HYDROGEN, HALOGEN, OR A LOWER ALKYL GROUP AND RII MAY BE AN ALKYL GROUP OF 1 TO 18 CARBON ATOMS, WHICH COMPRISES CONTACTING A HAOGENATING AGENT SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE, SULFURYL CHLORIDE, SULFURYL BROMIDE, N-CHLOROSUCCINIMIDE, AND N-BROMOSUCCINIMIDE WITH A COMPOUND OF THE FORMULA -CO-NH-RII WHEREIN Y IS HYDROGEN AN ALKYL GROUP OF 1 TO 18 CARBON ATOMS, AN ARALKYL GROUP OF UP TO 10 CARBON ATOMS, AN ARYL GROUP OF UP TO 10 CARBON ATOMS, A HALOGEN-, (C1-C4) ALKYL- OR (C2-C4)ALKOXY-SUBSTITUTED ARYL GROUP A DIALKYLAMINOALKYL GROUP OF UP TO 8 CARBON ATOMS, AN ALKOXYALKYL GROUP OF UP TO 8 CARBON ATOMS, AND ARYLOXYALKYL GROUP OF UP TO 12 CARBON ATOMS, OR A CARBAMOYL GROUP OF THE FORMULA 2-Y,3-(O=),4-R,5-R1-ISOTHIAZOLIDINE 1. A PROCESS FOR PREPARING ISOTHIAZOLONES OF THE FORMULA

Cross Sections for the Alkali‐Metal–Halogen Molecule Reactions: Cs with I2

Abstract: The reaction cross section of alkali‐metal atoms with halogen molecules is obtained by a direct measurement of the alkali‐atom decay rates. The alkali atoms are produced in the presence of a known amount of halogen molecules, by photodissociating an alkali halide salt with a short pulse of uv light. The alkali atoms react with the halogen molecules and the decay is monitored by observing the transmission of alkali‐atom resonance light through the vapor. Since the halogen density is known, the reaction cross section can be computed from the decay rate. Using this method we studied the reaction Cs+I2→CsI+I. The cross section for this process is 180 ± 25 A2.

Primary cell utilizing halogen-organic charge tranfer complex

Abstract: Primary cells capable of operating essentially in the solid state and utilizing reaction of a halogen with a metallic anode employ as cathode a charge transfer complex in which the acceptor component is the halogen and the donor component is an organic compound, typically aromatic or heterocyclic. Preferred anode materials include magnesium, calcium and barium. The maximum current produced by such cells can be increased by surrounding them with an atmosphere containing more than the normal partial pressure of water vapor, or containing vapor of an organic liquid such alcohol, acetone and acetonitrile, having a high dielectric constant. The physical properties of the charge transfer complex is improved by incorporating a polymeric matrix, which may or may not act also as the donor component of the complex.

1 4-dioxidoquinoxalinyl nitrones

Abstract: 1,4-DIOICXIDOQUINOXALINYL NITRONES HAVING THE FORMULA 1,4-DI(O=),2-(R1-N(=O)=CH-),3-(R2-),R3,R4-QUINOXALINE IN WHICH R1 IS AN ALKYL RADICAL OF 1 TO 10 CARBON ATOMS OF STRAIGH, BRANCHED OR CYCLIC CONFIGURATION WHICH MAY BE SUBSTITUTED WITH HYDROXY, DIHYDROXY, ALKOXY, ACLOXY, HALOGEN, OR TRIHALO GROUPS; OR R1 MAY BE A PHENYL RADICAL OR A PHENYL RADICAL SUBSTITUTED WITH A LOWER ALKYL GROUP OF 1 TO 4 GROUP CARBON ATOMS OR A HALOGEN; R2 IS HYDROGEN, LOWER ALKYL OF 1 TO 4 CARBON ATOMS, AND R3 AND R4 ARE CHOSEN FROM THE GROUP CONSISTING OF HYDROGEN, ALKOXY OR ALKYL OF 1 TO 4 CARBON ATOMS, HALOGEN, TRIHALOMETHYL, OR NITRO GROUPS. THESE NEW COMPOUNDS, WHICH ARE POTENT ANTIBACTERIAL AGENTS, ARE EFFECTIVE ORALLY, TOPICALLY AND PARENTERALLY IN LOW CONCENTRATIONS IN INHIBITING THE GROWTH OF BOTH GRAM-NEGATIVE AND GRAMPOSITIVE BACTERIA. THE COMPOUNDS MAY BE MADE BY REACTING AN APPROPRIATE 2-FORMYLQUINOXALINE 1,4-DIOXIDE WITH AN N-SUBSTITUTED HYDROXYLAMINE.

N.M.R. studies of aqueous solutions of alkali halides. II

Abstract: Chemical shifts of the nuclear resonances of 35Cl, 81Br and 127I in aqueous solutions of alkali halides (except LiI) from concentrations of about 0·5 molal up to saturation are recorded. The magnitude of the shifts increases with increasing atomic number of the halide ion and generally the shielding shows the following dependence upon the partner cation: At concentrations below 4 molal the shift of the halogen resonances varies approximately linearly with the mean activity of the salt for potassium, rubidium and caesium halides. Direct collisions between ions are the predominant cause of the chemical shifts of the halogen resonances in solutions of potassium, rubidium and caesium halides. In the lithium and sodium halide solutions the cation-water-halide ion interaction is of prime importance at concentrations below 8 molal. At greater concentrations direct interactions between the ions become increasingly important, giving rise to shifts to higher fields in lithium chloride solutions. Measurements of sol...

Lubricant comprising a novel lubricating improver of inorganic graphite fluoride

Abstract: Lubricants having excellent physical properties are composed of a base oil usually used and a high molecular weight inorganic graphite fluoride having a formula of (CF)n as an improver. Graphite fluoride is produced by reacting carbon or graphite with fluorine, halogen fluoride or a higher fluorine compound at a temperature of lower than 550* C.

Spectroscopy and photochemistry at low temperature. Part 3.—Photochemical production of ions and molecular complexes in dilute solutions of polyhalomethanes

Abstract: Transient products of the thermal decay of the colour centres which develop in frozen solutions of polyhalomethanes at 77 K on absorption of near u.-v. light, have been studied by means of u.-v. and visible spectroscopy at low temperatures. Absorption spectra of solvated trihalide ions have been detected, as well as those of weak complexes of molecular halogens with added olefins or with the polyhalomethane itself. The Aâ†�X absorption system of CF2 has been observed in viscous solutions of CF2Br2 at low temperature for the first time, and shown to be a product of the thermal decay of the colour centre. Halide ions are produced from all the polyhalomethanes, and could be formed following an electron transfer between neighbouring polyhalomethane molecules. Except for CF2Br2, little or no molecular halogen is released into solution unless it contains dissolved olefins. When molecular halogens are produced, their constituent atoms are both drawn from the same polyhalomethane molecule; they are products of a “molecular” reaction rather than association of free halogen atoms.

Process relating to ultra-pure metal halide particles

Abstract: Compositions are described including free-flowing particles of controlled size of purified metal halides such as sodium iodide and mixtures of sodium iodide with scandium iodide. These ultrapure metal halide particles are particularly useful as a vaporizable fill disposed within an arc tube of a high pressure electric discharge device. The preparation and identification of the coordination entity Na ScI 4 (III) is also described. The process for producing purified metal halides of accurately controlled particle size includes evaporating volatiles from the solid impure metal halide, melting the impure halide, passing hydrogen, hydrogen halide, hydrogen and halogen, or mixtures thereof through the halide, and then passing the molten halide through a vibrating discharge conduit or nozzle into an inert quenching atmosphere to form the particles of purified halide.

Studies of metal halides. III. Far-infrared spectra of chromium(III) and molybdenum(III) complex halides of formula A3M2X9 and A3MX6

Abstract: Far-infrared spectra are reported for compounds of formula A3M2X9, with M = Cr, Mo; X = Cl, Br; A = univalent cations, for the region 400-200 cm -1. Assignments for metal-terminal halogen and metal-bridging halogen stretching vibrations in the binuclear anion are proposed. Data on several related mono-nuclear hexahalo complexes are included for comparison. An explanation is offered for differences in the spectral features of the series of compounds in terms of distortions of the binuclear anion which arise from cation-anion interaction in the crystal lattice.

Gallium–gallium bonds in hexahalogenodigallate(II) ions

Abstract: The ions Ga2X62–(X = Cl, Br, or I), which contain a metal–metal bond and probably have ethane-like structures, are formed when gallium dissolves in halogen acids and have been isolated as crystalline Me4N+ salts.

Some reactions of electronically excited iodine atoms, I(52P½), with halides and oxides

Abstract: Electronically excited iodine atoms in the I(5p52P½) state, generated by the flash photolysis of CF3I in the gas phase, have been monitored by kinetic spectroscopy in absorption. The kinetics of the atoms were studied in the presence of a number of halides and oxides where the metathetical abstraction of halogen and oxygen atoms was exothermic and so, on thermochemical grounds, could compete with spin orbit relaxation. In the presence of the allyl halides and of nitrous oxide, the removal of I(52P½) was predominantly by collisional quenching, whereas with nitrosyl bromide and chloride, chemical reaction took place. The overall second-order rate constants for the decay of I(52P½) in the presence of the gases N2O, CH2CH—CH2Cl, CH2CH—CH2Br, CH2CH—CH2l NOCI and NOBr were 1.3 × 10–15, 1.3 × 10–13, 2.4 × 10–13, 4.2 × 10–13, 6.2 × 10–12 and 9.6 × 10–12 cm3 molecule–1 s–1 respectively, at ∼300 K. Vibrationally excited IO with up to four quanta in the ground electronic state, produced in the photolysis of CF3I + O3, results principally from the reaction of O(1D) with CF3I rather than that of I(52P½) with O3.

Sulfur containing heterocycles

Abstract: Halogen substituted 1,4-dithiane and 1,4-dithiene compounds are produced through the cycloaddition of bis-sulfenyl halides to acetylenic compounds. The reaction is conducted in the liquid phase at moderate temperatures and atomospheric pressure. The dithiane and dithiene compounds may be employed as lubricating oil additives and as precursors to insecticidal toxicants.

Behaviour of electron acceptors in low-pressure acetylene oxygen flames

Abstract: Introduction of small proportions of electron acceptors such as chlorine or bromine into low-pressure acetylene + oxygen flames results in a marked reduction of the free electron concentration in the reaction zone. Quantitative studies of this effect by the cyclotron resonance technique suggest strongly that for halogen it is caused principally by formation of negative halide ion, B–, through the balanced process HB + e–⇌ H + B–. The results are also shown to yield information about the extent of disequilibrium in the reaction zone. On the basis of this mechanism, the electron affinities of chlorine and bromine are deduced to be 83.0 ± 0.5 and (E.A.CI–4.5)± 0.5 kcal/mole respectively, which are in satisfactory agreement with the values of 83.33 and 77.55 kcal/mole obtained by Berry and Reimann through a photodetachment procedure. Traces of cyanogen, sulphur compounds and ammonia also produce large reductions in electron concentrations. Possible explanations of these effects in terms of electron acceptors are considered.

Process of joining lithiated polymers or copolymers

Abstract: Polymers of increased molecular weight are produced from plastic and/or rubbery polymers derived from vinylidene monomers by reaction with an organic halogen compound in the presence of an alkali metal hydrocarbon and also in the presence of an accelerator which is a Lewis base. The reactant polymers include polystyrene and similar plastic polymers and rubbery polymers such as polybutadiene and butadiene-styrene copolymers. The organic halogen compound is any carbon compound containing at least one reactive halogen atom per molecule. The halogen is fluorine, chlorine, bromine and/or iodine. The alkali metal hydrocarbon is preferably a ''''live'''' polymer containing reactive alkali metal, e.g., polybutadiene produced by polymerization of butadiene-1,3 by means of a lithium initiator. The Lewis base may be organic or inorganic, but it is preferred to use organic compounds and especially ethers. Preferred products are nonflow rubbery polymers.