- Near threshold photofragmentation dynamics of ICl-Ne A state van der Waals complexes
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The nascent ICl product state distribution is examined following vibrational predissociation of ICl-Ne A(νA=23) complexes via an optical-optical double resonance technique.ICl fragments are produced in approximately equal proportion in the νA=22 and 21 levels of the A(3Π1) state.Low rotational levels of ICl A(νA=22) are primarily populated, JA=1-8, accesing only a small portion of allowed states.ICl A(νA=21) fragments are produced with up to 69 cm-1 of rotational energy in a broad distribution which extends to nearly the energetic limit.Homogeneous broadening of the ICl-Ne feature indicates a vibrational predissociation lifetime between 2.3 and 50 ps.
- Drobits, Janet C.,Lester, Marsha I.
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Read Online
- I(2P1/2) Deactivation by ICl and Cl2
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The rates of deactivation of I(2P1/2) by ICl and Cl2 have been measured in a fast-flow apparatus.The rate constant obtained for deactivation by ICl is fast (k = 1.5E-11 cm3 molecule-1 s-1) and is in good agreement with previous determinations by other workers.The rate constant obtained for deactivation by Cl2, however, is much slower (k = 1.7E-14 cm3 molecule-1 s-1) and is in contrast to earlier determinations by other workers, using static bulb techniques, who report much faster rates.Possible reasons for the discrepancy are advanced, and a possible mechanism to account for the fast deactivation by ICl is suggested.
- Lilenfeld, H. V.,Whitefield, P. D.,Bradburn, G. R.
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Read Online
- Preparation method of hexafluorobutadiene
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The invention relates to a preparation method of hexafluorobutadiene, and belongs to the technical field of fluorine-containing gas preparation. The preparation method comprises the following steps: preparing a polar base solution, activated zinc and 1,2-dichloro2iodo-1,1,2-trifluoroethane, further preparing 1,2,3,4-tetrachlorohexafluorobutane, and finally preparing hexafluorobutadiene. Accordingto the method, activated zinc is used in the preparation process and is matched with a polar base solution serving as a solvent, so that the reaction rate is increased, the yield and selectivity of 1,2,3,4-tetrachlorohexafluorobutane are guaranteed; therefore, the problem that the reaction rate is influenced by using zinc particles which are not activated and have larger particles and adopting a solvent with poorer polarity in the prior art is solved; in addition, a non-polar solvent and activated zinc are added in the preparation of hexafluorobutadiene, so that byproducts generated in the preparation process of hexafluorobutadiene are easier to separate while the yield and selectivity of hexafluorobutadiene are ensured.
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Paragraph 0039; 0045-0046; 0052; 0057-0059; 0064; 0069-0071
(2021/01/29)
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- Method for preparing hexafluorobutadiene from iodine and chlorine
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The invention relates to a method for preparing hexafluorobutadiene from iodine and chlorine. The method comprises the following steps: preparing a metal coordinated ionic liquid solvent, and reacting iodine with chlorine to prepare iodine monochloride; reacting iodine monochloride with chlorotrifluoroethylene in the presence of the metal coordinated ionic liquid solvent to prepare 1,2-dichloro-2-iodo-1,1,2-trifluoroethane; carrying out a reaction on the 1,2-dichloro-2-iodo-1,1,2-trifluoroethane in the presence of the metal coordinated ionic liquid solvent under the catalysis of zinc powder to obtain 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane; and reacting the 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane with zinc powder in the presence of the metal coordinated ionic liquid solvent to generate hexafluorobutadiene.
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Paragraph 0034-0035; 0045-0046; 0056-0057
(2017/08/27)
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- Tricyclic pyridine derivatives, medicaments containing such compounds, their use and process for their preparation
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The present invention relates to compounds defined by formula I wherein the variables R1-R8 are defined as in the description, possessing valuable pharmacological activity. Particularly, the compounds are inhibitors of cholesterol ester transfer protein (CETP) and thus are suitable for treatment and prevention of diseases which can be influenced by inhibition of this enzyme.
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Paragraph 1083; 1084; 1085; 1086
(2013/03/26)
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- Stabilizing aqueous solution of iodine chloride by adding sodium chloride
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This invention relates generally to non-ionic X-ray contrast agents. It further relates to the preparation of iodine chloride, a key reagent in the synthesis of non-ionic X-ray contrast agents such as iodixanol and iohexol. In particular, the iodine chloride is produced in a reaction involving iodine, sodium chlorate, and hydrochloric acid as the starting materials. The instant invention relates to a method of stabilizing aqueous iodine chloride solutions by adding about one to about four molar equivalents of sodium chloride relative to sodium chlorate to an aqueous reaction mixture of sodium chlorate, hydrochloric acid, and iodine.
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Page/Page column 3
(2011/02/19)
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- Obtaining free iodine in preparation of aqueous iodine chloride by adding potassium iodide
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This invention relates generally to the preparation of non-ionic X-ray contrast agents, iohexol, ioversol, and iodixanol. It further relates to an improved method for the iodination reaction, a key step in the industrial preparation of non-ionic X-ray contrast agents. In particular, it relates to a method for producing free iodine in an aqueous solution of iodine chloride by adding minor amounts of potassium iodide.
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Page/Page column 4
(2011/02/19)
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- Design and synthesis of nonpeptidic, small molecule inhibitors for the Mycobacterium tuberculosis protein tyrosine phosphatase PtpB
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The design and synthesis of new inhibitor analogues for the Mycobacterium tuberculosis (Mtb) phosphatase PtpB is described. Analogues were synthesized by incorporation of two common and effective phosphate mimetics, the isothiazolidinone (IZD) and the difluoromethylphosphonic acid (DFMP). The basic scaffold of the inhibitor was identified from structure-activity relationships established for a previously published isoxazole inhibitor, while the phosphate mimetics were chosen based on their proven cell permeability and activity when incorporated into previously reported inhibitors for the phosphatase PTP1B. The inhibitory activity of each compound was evaluated, and each was found to have low or submicromolar affinity for PtpB.
- Rawls, Katherine A.,Grundner, Christoph,Ellman, Jonathan A.
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p. 4066 - 4070
(2010/10/05)
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- Ion-detecting sensors comprising plasticizer-free copolymers
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Ion-detecting sensors for detecting a target ion in a sample are provided. The sensor comprises a plasticizer-free copolymer comprised of polymerized units of methacrylate monomers having pendent alkyl groups of different length and a functionalized ionophore of said ion, wherein at least a portion of the functionalized ionophore is grafted into the copolymer through covalent linkages. Sensors may comprise ionophores such as hydrophilic crown ethers or functionalized derivative of 3-oxapentandiaminde-type ionophores. This invention further provides sensors for detecting target ions in a sample, comprising plasticizer-free molecularly imprinted polymers, wherein the polymers comprise polymerized units of methacrylate monomers having pendent alkyl groups of different length and a functionalized ionophore of said ion. In particular, a magnesium ion sensor comprising a functionalized derivative of a 3-oxapentandiaminde-type calcium ion-selective ionophore is provided. Sensors of this invention include carrier-based ion-selective electrodes or optodes such as thin film ion-specific optodes, particle-based optodes, or bulk optodes.
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- A facile synthesis of 1,4-dialkoxy-2,5-diiodobenzenes: reaction of dialkoxybenzenes with iodine monochloride in alcoholic solvents
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A facile synthesis of 1,4-dialkoxy-2,5-diiodobenzenes via diiodination of the corresponding dialkoxybenzenes with iodine monochloride has been developed. Employment of ah alcoholic solvent as a reaction medium is crucial for attaining a high yield; the reaction in a nonalcoholic solvent usually resulted in a poor yield. The diiodobenzene derivatives are useful intermediates in the synthesis of such advanced materiais as soluble phenylenevinylene polymers anal dialkoxy derivatives of 7,7,8,8-tetracyanoquinodimethane.
- Wariishi, Koji,Morishima, Sin-Ichi,Inagaki, Yoshio
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- Heterogeneous reaction of HOI with sodium halide salts
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The interaction of gaseous HOI with crystalline grains of NaCl and sea-salt and thin films of NaBr crystals has been studied in a wall coated tubular flow reactor coupled to a quadrupole mass spectrometer over a concentration range (0.2-8) × 1012 molecules cm-3 at 278 and 298 K. On a fresh surface, the uptake coefficients determined were independent of temperature with γ = 0.034 ± 0.009, γ = 0.016 ± 0.004, and γ = 0.061 ± 0.021 for NaBr, NaCl, and sea-salt, respectively. No increase in reactivity was observed on addition of water vapor between 0 and 23% relative humidity at 278 K. It was also shown that the reactivity of the salt surface decreased with time of exposure to HOI and that steady-state uptake was slower on aged salt surfaces. Products of the reactions released into the gas phase were IBr, ICl, and IBr + ICl for the reaction of HOI on NaBr, NaCl, and sea-salt surfaces, respectively. The atmospheric implications of the results obtained are briefly discussed.
- Moessinger, Juliane C.,Cox, R. Anthony
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p. 5165 - 5177
(2007/10/03)
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- Process for making dihalodifluoromethanes and their homologues
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Highly fluorinated epoxides are reacted with dihalogens in the presence of metal and metal containing reaction promoters to give dihalofluoromethanes and their homologues.
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- Novel Investigation on the Crystal Structure of α-ICl
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The redetermination of the crystal structure of α-iodine monochloride, α-ICl, is described. It crystallises monoclinically in the space group P21/c with a = 1216.2(1), b = 428.6(1), c = 1188.9(1) pm, β = 117.50(1)° and eight formula units per unit cell.
- Minkwitz, Rolf,Berkei, Michael
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p. 1615 - 1617
(2007/10/03)
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- Preparation, characterisation, quantum chemical calculations, and chemical reactions of sulfurdiimine, its silver and thallium salts as well as TlNSO
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Reactions of (CH3)3SiNSNSi(CH3)3 with Ag[CF3C(O)O] or TlF respectively have allowed the formation of the highly explosive compounds M2[SN2] (M = Ag, Tl) in nearly quantitative yields. Under analogous conditions (CH3)3SiNSO and TlF formed non-explosive TlNSO again in about 100% yield. The reaction between (CH3)3SiNSNSi(CH3)3 and ICl was found to be easily reproducable and gave INSNI in good yields. INSNI was obtained also from K2[SN2] and ICl in 40% yield. The reaction of (CH3)3SiNSNSi(CH3)3 with CsF resulted in monosubstitution and the formation of CsNSNSi(CH3)3. INSNI reacted with HX (X = Cl, I) in closed systems to give S4N4, NH4X, IX and N2 as final products. Similar results were observed when M2[SN2] was treated with HX in Carius tubes. Besides higher yields of S4N4 small amounts of S4N3Cl and other not identified SN compounds were detected. In open systems HX reacted with M2[SN2] in dynamic vacuo explosively. Under matrix conditions preliminary tests showed that TlNSO formed with HX pure HNSO, characterised by a high quality matrix IR-spectrum. With the help of this metathetical reaction, the conditions for matrix-spectroscopic studies of the system MNSNM and HX could be optimized. If M2[SN2] was treated with HX analogously HNSNH was produced. The diimine was characterized by bands of comparable intensities, appearing in spectra of the products of the reaction which were assigned to the molecule. Identical bands were also observed when INSNI was treated with excess HX. If the procedure was carried out with 1:1 molar quantities, the formation of the primary produced HNSNI could be evidenced by IR-spectroscopy. Detailed quantum chemical ab inition calculations about structures, relative energies and vibrational spectra of the HNSNH-conformers as well as other possible SN2H2 isomeres were carried out. They confirmed the experimental results and assignments and strengthened the conclusion that HNSNH was present as a mixture of E,Z- and Z,Z-conformers.
- Haas, Alois,Fleischer, Ulrich,Maetschke, Matthias,Staemmler, Volker
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p. 681 - 692
(2008/10/08)
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- Poly-iodinated compounds, process for their preparation, contrast medium containing them
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The invention relates to novel poly-iodinated compounds of general formula: STR1 in which R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, identical or different, are selected from an iodine atom, a group of formula STR2 provided that at least two of the R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 groups represent an iodine atom, utilizable in contrast media for radiography. The invention also relates to a process for the preparation of these compounds as well as a contrast medium containing them.
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- Kinetics of the IO radical. 1. Reaction of IO with ClO
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The rate coefficient for the IO + ClO → products (5) reaction was measured by coupling discharge flow and pulsed laser-induced fluorescence techniques. Rate coefficients were measured from 200 to 362 K by monitoring the temporal profile of IO in an excess of ClO. The rate coefficient is described by the expression: k5(T) = (5.1 ± 1.7) × 10-12 exp[(280 ± 80)/T] cm3 molecules-1 s-1 where the quoted uncertainties include estimated systematic errors. Atomic iodine was identified as a major product of reaction 5. A branching ratio of Φ = 0.14 ± 0.04 at 298 K was obtained for the sum of channels which do not produce I atoms.
- Turnipseed, Andrew A.,Gilles, Mary K.,Burkholder, James B.,Ravishankara
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p. 5517 - 5525
(2007/10/03)
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- Rate constants and equilibrium constants for X + CF3I ? CF3 + IX, where X = Br, C1
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Equilibrium constants for X + CF3I ?k(-1)k(1) CF3 + XI, where X = Cl or Br, have been calculated from molecular constants of CF3I, IBr, and IC1 using statistical thermodynamics. The rate constant of the direct reaction for X ≡ Br has been measured by the temperature-jump method. Rate constants of the reverse reactions have been calculated.
- Dymov,Skorobogatov,Khripun
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p. 714 - 719
(2008/10/08)
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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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- Non-metal redox kinetics: Oxidation of iodide by hypochlorous acid and by nitrogen trichloride measured by the pulsed-accelerated-flow method
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The very rapid reaction between HOCl and I- is general-acid- (HA-) assisted. The proposed mechanism is HOCl + I- ?k-1k1 HOClI- HOClI- →k0 HO- + ICl HOClI- + HA →kHA H2O + ICl + A- ICl + 2I- →fast I3- + Cl- where a stability constant (k1/k-1 = 220 M-1) is determined for the HOClI- intermediate from kinetic data and the limiting rate constant at high [H+] is k1 = 4.3 × 108 M-1 s-1. Values for third-order rate constants (with the general form k1kHA/(k0 + k-1) (M-2 s-1) at 25.0°C, μ = 0.1) are evaluated for H3O+ (3.5 × 1011), CH3COOH (3.2 × 1010), and H2PO4- (2.6 × 1010) and give a Br?nsted α value of 0.11, which indicates a small degree of proton transfer in the transition state. For the H2O path, k0k1/(k0 + k-1) = 1.4 × 108 M-1 s-1. The reaction between trichloramine and iodide exhibits saturation kinetics due to the formation of NCl3I- (K1 = 6 × 103 M-1), which undergoes first-order decomposition (k2 = 1.5 × 104 s-1 at 25.0°C and μ = 0.1) to HNCl2 and ICl. Acids do not affect the rate of NCl3I- decomposition. For these two studies first-order rate constants fall in the range of 10 000-142 000 s-1 and are measured by pulsed-accelerated-flow spectroscopy.
- Nagy, Julius C.,Kumar, Krishan,Margerum, Dale W.
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p. 2773 - 2780
(2008/10/08)
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- Slow chain reactions of Br2 and Cl2 with HI: Multiple state analysis and vibrational relaxation of HBr(v = 2) and HCl(v = 1 - 4)
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Two chain reactions of the general form are studied by realtime detection of infrared chemiluminescence from the vibrationally excited HX(v) products.Both are characterized by k2 a flow cell apparatus at 295 K.Observations are made on Δv = -1 fluorescence from individual vibrational levels, and the results are treated with a complete mathematical analysis for the production of multiple vibrational states and their subsequent individual decays.Effects of vibrational cascading on the measurements of k2 are discussed.The chain propagation rate coefficients determined by this technique for k1(X = Br, Cl) and k2(X = Br, Cl) are 8.9(+/- 1.3) * 10-12, 1.4(+/- 0.3) * 10-10, 3.4(+/- 0.8) * 10-13, and 8.5(+/- 1.1) * 10-17 cm3 molecule-1 s-1, respectively.The deactivation rate coefficients for HBr(v = 2) and HCl(v = 1,2,3,4) by HI are 1.7(+/- 0.2) * 10-12, 1.43 (+/- 0.05) * 10-13, 6.3(+/- 0.5) * 10-13, 7.0(+/- 2.4) * 10-13, and 3.2(+/- 0.7 * 10-12 cm3 molecule-1 s-1, respectively.Vibrational deactivation rate cofficients for HCl(v = 1,2,3,4) by Cl2 are 5.2(+/- 0.3) * 10-15, 2.2(+/- 0.3) * 10-14, 4.3(+/- 4.2) * 10-14, and 2.8(+/- 1.5) * 10-13 cm3 molecule-1 s-1, respectively.The vibrational deactivation efficients of HCl(v = 1 - 4) by HI and Cl2 scale approximately as vn, where n = 2.1(+/- 0.2) and 2.8(+/- 0.2), respectively.
- Dolson, David A.,Leone, Stephen R.
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p. 4009 - 4021
(2007/10/02)
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- Millimetr wave measurements of the rotational spectra of ClF, BrF, BrCl, ICl, and IBr
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The rotational spectra of all twelve stable isotopic species of ClF, BrF, BrCl, ICl, and IBr were abserved and measured in the millimeter wave region by means of a sensitive microwave spectrometer.Transitions were detected over a wide range of frequencies for molecules in both the ground vibrational state and several excites states.The rotational spectrum of each molecule was split by the nuclear quadrupole interaction.Altogether, 250 new lines were measured.These correspond to 136 purw rotational transitions.Values of the Dunham coefficients Y01, Y11, Y21, Y31, Y02, Y12, and Y03 were obtained from a computer analysis of the measured frequencies.From these coefficients a number of equilibrium constants were derived to significantly greater accuracy than in previous work.In particular, the equilibrium distance, re, was found to two or three more significant figures.
- Willis, Robert E.,Clark, William W.
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p. 4946 - 4950
(2007/10/02)
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