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1.
The (19)F NMR spectra of a series of fluorinated cyclopropanes, most of which contain chlorine or bromine on the ring, have been observed and analyzed. A scheme has been developed to assign the resonances and the molecular stereochemistry, based on substituent effects, comparison of related molecules, and isotope shifts induced by the halogens. Replacement of fluorine by chlorine shifts cis fluorine resonances to lower field, and bromine has an even greater downfield influence. However, the shift effect of bromine compared to chlorine on gem or trans fluorines is variable. The magnitude of the isotope shifts is found to be regularly related to the geometrical relationship of the halogen to the observed fluorine and thus makes a significant contribution to the fluorine assignments. The three-bond spin-spin coupling constants between fluorine atoms in cyclopropanes display unusual behavior and are not helpful for assignment of the fluorine resonances. The signs of the coupling constants have been investigated by spin-tickling experiments, and the previously developed relation of the coupling constant sign to its temperature dependence has been found to be violated for some molecules. 相似文献
2.
The interactions of nitrous oxide with fluorinated liquids are investigated by reporting original experimental results on gas solubility and interpreting them using molecular simulation. Nitrous oxide is highly soluble in the three fluorinated liquids studied-perfluorooctane, 1-bromoperfluorooctane (perfluorooctylbromide), and perfluorohexylethane-with mole fraction solubilities on the order of 0.03 under ambient conditions. An intermolecular potential model was developed for nitrous oxide, with a functional form of the Lennard-Jones plus point charges type, adjusted to the experimental multipole moments and to vapor-liquid equilibrium properties. The solubility of nitrous oxide in perfluorocarbon liquids was calculated by molecular simulation methods, and a dissimilar interaction parameter of 0.92 in the Lennard-Jones well-depths between solute and solvent had to be introduced to reach agreement with the experimental results, similar to what is found for hydrocarbon-fluorocarbon interactions. The structure of the solutions was studied by analysis of solute-solvent radial distribution functions, showing that, although electrostatic interactions are not predominant, a small orientational effect is still present between the dipole of nitrous oxide and those of the substituted fluorinated liquids. 相似文献
3.
Diffusion coefficients of atomic halogen with noble gases were calculated from the potential curves reported in the literature from the crossed molecular-beam scattering experiments. The deviations of the diffusion constants between the atomic halogen-noble gas systems and the neighboring noble gas-noble gas systems were obtained over the temperature range of 200 K to 1100 K. The parameters of Lennard-Jones 6–12 potentials were also obtained for the chlorine and iodine atoms. The internal consistency of the diffusion constants calculated from the 6–12 potential parameters among the halogen atom-noble gas systems is very good. However, the agreement was found to be only fair for the inert molecular systems with the chlorine atoms. The extent of the similarity of the diffusion constants between the atomic halogen-noble gas and the noble gas-noble gas systems is discussed. 相似文献
4.
Bunyard WC Kadla JF DeYoung J DeSimone JM 《Journal of the American Chemical Society》2001,123(30):7199-7206
The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, k(obs), increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The k(obs) values are comparatively larger in dense carbon dioxide and similar to the "zero-viscosity" rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects. 相似文献
5.
The interactions of oxygen and of carbon dioxide with normal and brominated octane are studied by analysing original experimental gas solubility data as a function of temperature in the range between 288 and 313 K. The temperature dependence of the solubility yields the thermodynamic properties of solvation. The influence of bromine substitution was studied by comparing the present data with that for perfluorooctane and 1-bromoperfluorooctane. A molecular interpretation of the effects observed was done using atomistic simulation. In order to simulate 1-bromooctane, parameters of the molecular force field were developped for bromoalkanes within the OPLS-AA framework. In general, simulation provides correct predictions of the solubility and of its temperature dependence, except in cases where values are too close (within the error bars of the simulation). Structural aspects of the solvation of the two gases were analysed in light of the site–site solute–solvant radial distribution functions. The relative importance of electrostatic interactions is assessed by modifying the intermolecular potential models for the gases. 相似文献
6.
Edmund Elce Allan S. Hay 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1143-1151
Two novel fluorinated monomers were prepared and polymerized with biphenols to produce amorphous, thermally stable poly(aryl ether ketone)s. The properties of the fluorinated polymers are compared to those of unfluorinated, amorphous poly(aryl ether ketone)s. The presence of fluorine in the polymers was found to cause a decrease in glass transition temperature and Young's moduli, however, no increase in thermal stability was observed. The fluorinated polymers are soluble in common organic solvents such as chloroform and methylene chloride at room temperature, and also show solubility in solvents containing a ketonic moiety, such as acetone. Evidence of polymer branching through fluorines considered to be unreactive under the polymerization conditions was found. Efforts were made to evaluate the reactivity of fluorine atoms under the polymerization conditions using both molecular modeling and 19F-NMR to ascertain if such branching could be avoided. © 1995 John Wiley & Sons, Inc. 相似文献
7.
Effect of halogen bonding on supramolecular assembly and photophysical properties of diaryl oxalates
Dong-En Wu Yang-Hui Luo Man-Ning Wang Qing-Ling Liu Gao-Ju Wen Ling-Jun Zhu Chang-Po Fan Bai-Wang Sun 《Structural chemistry》2017,28(6):1731-1742
In order to determine the effect of halogen bonding on supramolecular assemblies and photophysical properties of diaryl oxalates, diaryl oxalate itself and its derivatives with fluorine, chlorine, bromine, and iodine substituents in the p-position of phenyl rings were studied and compared. Their single-crystal structures were studied by geometrical analysis and theoretical calculation. The study reveals that different halogen bonds are formed with respect to different halogen atoms, such as C…F and X…X (bromine and iodine atoms) interactions, and molecular stacking modes would be affected by halogen bonds directly. Comparative studies of photophysical properties in dilute solution and solid state indicate that halogen substitutions would not affect the emission processes of diaryl oxalates in dilute solution; this is not the case for their solid state. This work has demonstrated that halogen bonds play an important role in regulating structures and photophysical properties of diaryl oxalates. 相似文献
8.
《The Journal of chemical thermodynamics》2007,39(6):847-854
The solubility of oxygen, carbon dioxide, and carbon monoxide in three fluorinated liquids – perfluorohexylethane, perfluorooctane and bromoperfluorooctane – is presented. Mole fraction solubilities were calculated from new experimental Ostwald coefficient data for CO2 and CO, and from previously published values for O2, associated with original values of density and vapour pressure for the pure solvents. Carbon dioxide is the most soluble gas with mole fraction solubilities of the order of 10−2. Oxygen and carbon monoxide are one order of magnitude less soluble. The measurements were done as a function of temperature between (288 and 313) K and from the variation of the calculated Henry’s law constants with temperature, the thermodynamic properties of solvation such as the Gibbs free energy, the enthalpy and the entropy were calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry’s law constants from appropriate smoothing equations is of 1% for carbon dioxide and oxygen and of 3% for carbon monoxide. The data obtained here are judged accurate to within ±5%. 相似文献
9.
Lorenzo Tattini Pierandrea Lo Nostro Luca Scalise Barry W. Ninham Piero Baglioni 《Journal of colloid and interface science》2009,339(1):259-265
Diblock semifluorinated n-alkanes can form aggregates and gels in fluorinated solvents. We have investigated the thermal behavior of binary mixtures comprising F(CF2)8(CH2)16H and fluorinated solvents. The solvents were perfluorohexane, perfluoroheptane, perfluorooctane, perfluorooctyl bromide, perfluorodecalin, and perfluorotributylamine. The phase diagrams were used to calculate the activity coefficients of the two components and the main excess thermodynamic functions. The solubility and self-assembly behavior of F8H16 in the fluorinated solvents are related to the different solute–solvent dispersion interactions that depend on the polarizabilities and ionization potentials of the interacting species, and on the structural properties of the solvent. 相似文献
10.
Alexey V. Gutov Eduard B. Rusanov Alexey B. Ryabitskii Alexander N. Chernega 《Journal of fluorine chemistry》2010,131(2):278-281
The structure and chemical properties of perfluoro-4,4′-bipyridine have been studied. It was found that octafluoro-4,4′-bipyridine is a quite electron deficient system stable to the action of alkylating agents and sensitive to nucleophilic substitution of fluorine atoms. Depending on the reaction conditions and reagents used products could be obtained in which two and six fluorine atoms are substituted by nucleophiles. For all isolated compounds X-ray structure determination has been performed and the main peculiarities of the molecular and crystal structure of fluorine-containing bipyridines have been determined. 相似文献
11.
A series of halogen-containing aromatic polyesters with decamethylene-spacer groups was synthesized by the solution polymerization from 4,4′-dicarboxyl-1,10-diphenoxy-decane and bisphenol A. Incorporation of fluorine atoms in the bisphenol A units in the polymer backbone enhanced the solubility of the polyesters in various organic solvents, as did the substitution of chlorine and bromine on the aromatic rings of the bisphenol A, ortho to the ester linkages. The effect of the halogen substituents on the thermal and radiation sensitivities of the polyesters has been investigated. The inherent viscosities of THF solutions at 30°C ranged from 0.25 to 0.63 dL/g. The number average (6,000∼31,000) and weight average molecular weights (12,000∼48,000) were measured by gel permeation chromatogrpahy, resulting in polydispersity indices of M2/Mn=1.6∼2.0. The chemical structures of the polyesters were characterized by means of IR spectroscopy, 1H NMR and 13C NMR spectroscopies and elemental analyses. All the results were in good agreement with the expected formula. Comparison of 13C NMR spectra of the polymers aided in the assignments of the structures. Only the unsubstituted polyester derived from bisphenol A was found to be semicrystalline by X-ray diffraction and DSC measurements, with a crystalline melting temperature of 160°C. The glass transition temperatures of the polyesters was found to be dependent on the size of the halogen substituent on the repeating units, and ranged from 77 to 140°C. The thermal stabilities of the polyesters showed a dependence on the nature of the halogen substituent, as did the high energy radiation sensitivites of the polymers, as assessed by the yields of radicals at 77 K. © 1998 John Wiley & Sons, Ltd. 相似文献
12.
Corine Bas Rgis Mercier Jos Sanchez‐Marcano Sylvie Neyertz N. Dominique Albrola Eliette Pinel 《Journal of Polymer Science.Polymer Physics》2005,43(17):2413-2426
A series of polyimides with alicyclic and fluorinated moieties previously synthesized were studied for gas separation applications. The solubility behavior of polyimides in various solvents was analyzed through the solubility parameter approach. Permeability coefficients and ideal selectivities were determined for common gases, that is, He, H2, O2, and N2. Polyimide permeabilities were correlated to an improvement of the soluble character and were increased by the introduction of both alicyclic and fluorinated structures. The effect of the casting solvent on gas separation properties was also pointed out. It was found that it is enhanced with increasing diameters for the gas molecules. Finally, some correlations between permeability coefficients and microstructural parameters were discussed. The probability of correlation appears to be also dependent on the diameter and on the polarizability of the gas molecule. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2413–2426, 2005. 相似文献
13.
Hiroaki Shimomoto Dai Fukami Tomomi Irita Ken‐ichi Katsukawa Takabumi Nagai Shokyoku Kanaoka Sadahito Aoshima 《Journal of polymer science. Part A, Polymer chemistry》2012,50(8):1547-1555
Various types of fluorine‐containing star‐shaped poly(vinyl ether)s were successfully synthesized by crosslinking reactions of living polymers based on living cationic polymerization. Star polymers with fluorinated arm chains were prepared by the reaction between a divinyl ether and living poly(vinyl ether)s with fluorine groups (C4F9, C6F13, and C8F17) at the side chain using cationogen/Et1.5AlCl1.5 in a fluorinated solvent (dichloropentafluoropropanes), giving star‐shaped fluorinated polymers in high yields with a relatively narrow molecular weight distribution. The concentration of living polymers for the crosslinking reaction and the molar feed ratio of a bifunctional vinyl ether to living polymers affected the yield and molecular weight of the star polymers. Star polymers with block arms were prepared by a linking reaction of living block copolymers of a fluorinated segment and a nonfluorinated segment. Heteroarm star‐shaped polymers containing two‐ or three‐arm species were synthesized using a mixture of different living polymer species for the reaction with a bifunctional vinyl ether. The obtained polymers underwent temperature‐induced solubility transitions in various organic solvents, and their concentrated solutions underwent sol–gel transitions, based on the solubility transition of a thermoresponsive fluorinated segment. Furthermore, a slight amount of fluorine groups were shown to be effective for physical gelation when those were located at the arm ends of a star polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
14.
The retention behaviour of several gaseous fluorinated greenhouse gases on carbon-based adsorbents is presented. Retention, calculated on the basis of compound breakthrough volume (BTV), is dependent on the molecular composition of the adsorbate, with compounds possessing chlorine or polarizable hydrogens being better retained than those possessing higher fluorine content. Of the adsorbents tested the carbon molecular sieves (CMSs) of highest surface area show greater retention than those with lower area. Retention of fluorocarbons is generally higher on activated charcoals but this adsorbent type can cause irreversible retention, possible degradation and is more difficult to use practically due to its heterogeneous composition. These breakthrough volume results can be used to determine the best combination and quantities of each adsorbent that can be used within a preconcentration device with a view to developing an analytical system for the determination of fluorocarbon gases in low concentration air samples. 相似文献
15.
E. D. Totchasov M. Yu. Nikiforov G. A. Al’per 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(10):1623-1626
A method for calculating the solubility of gases in mixed nonaqueous solvents was suggested. The method was based on the theory of molecular association and the simple lattice model. It allowed the solubility of gases in mixed nonaqueous solvents to be calculated only using molecular association parameters and the mutual exchange energy ωAB determined from the data on phase equilibria in mixed solvents. 相似文献
16.
Masafumi Kobayashi Tetsuya Inoguchi Takashi Iida Takashi Tanioka Hiroshi Kumase Yasushi Fukai 《Journal of fluorine chemistry》2003,120(2):2838-110
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride. 相似文献
17.
Hiroaki Shimomoto Dai Fukami Shokyoku Kanaoka Sadahito Aoshima 《Journal of polymer science. Part A, Polymer chemistry》2011,49(9):2051-2058
Partially fluorinated poly(vinyl ether)s with C4F9 and C6F12H groups in the side chain were synthesized via living cationic polymerization in the presence of an added base in a fluorine‐containing solvent, dichloropentafluoropropanes. For comparison, the polymerization of vinyl ether monomers with C2F5 and C6F13 groups and nonfluorinated monomers were also carried out. The characterization of the product polymers using size exclusion chromatography with a fluorinated solvent as an eluent indicated that all polymers had narrow molecular weight distributions (Mw/Mn ~ 1.1). Interestingly, the moderately fluorinated polymers with C4F9 exhibited upper critical solution temperature‐type phase separation in various organic solvents with wide‐ranging polarities, whereas highly fluorinated polymers with C6F13 are insoluble in nonfluorinated solvents. Polymers with C4F9 groups exhibited temperature dependent solubility transitions not only in common organic solvents (e.g., toluene, chloroform, tetrahydrofuran, and acetone) but also in perfluoro solvents [e.g., perfluoro(methylcyclohexane) and perfluorodecalin]. On the other hand, the solubility of polymers with C6F12H showed completely different from that of polymers with C6F13, despite their similar fluorine content. In addition, various types of fluorinated block copolymers were prepared in a living manner. The block copolymers with a thermosensitive fluorinated segment underwent temperature‐induced micellization and sol–gel transition in various organic solvents. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
18.
Here we reported a novel and efficient method for the synthesis of the critical intermediates of branched fluorinated surfactants with CF3CF2CF2C (CF3)2- group using HFPD as starting material. The reaction conditions were mild and easy to handle, which was promisingly applied to the industrial production. 相似文献
19.
Hiroaki Shimomoto Dai Fukami Shokyoku Kanaoka Sadahito Aoshima 《Journal of polymer science. Part A, Polymer chemistry》2011,49(5):1174-1182
Living cationic polymerization of fluorine‐containing vinyl ethers [CH2?CH? O? C2H4? O? C3H6? CnF2n+1: 5FVE (n = 2), 13FVE (n = 6)] was investigated in various solvents with a CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5 initiating system in the presence of an added base. 5FVE was polymerized quantitatively in toluene at 0 °C, and the obtained polymers had predetermined molecular weights with narrow molecular weight distributions (Mw/Mn < 1.1). On the other hand, for the polymerization of 13FVE, the product polymers precipitated due to their extremely poor solubility in nonfluorinated organic solvents. Therefore, fluorinated solvents such as hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroethers, or α,α,α‐trifluorotoluene, as‐yet uninvestigated for cationic polymerization, were employed. In these solvents, living polymerization was achieved even with 13FVE, yielding well‐defined polymers (Mw/Mn < 1.1, by size exclusion chromatography using a fluorinated solvent as an eluent). The solvents were also shown to be good for living polymerization of isobutyl vinyl ether. The obtained fluorine‐containing polymers underwent temperature‐responsive solubility transitions in organic solvents. Poly(5FVE) showed sensitive upper critical solution temperature (UCST)‐type phase separation behavior in toluene. Copolymers of 13FVE and isobutyl vinyl ether showed UCST‐type phase separation in common organic solvents with different polarities depending on their composition, while a homopolymer of 13FVE was insoluble in all nonfluorinated organic solvents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
20.
L. Conte G. P. Gambaretto M. Napoli C. Fraccaro E. Legnaro 《Journal of fluorine chemistry》1995,70(2):175-179
The fluorination of aromatic compounds (benzene, toluene, phenol and benzoic acid) by elemental fluorine diluted with nitrogen has been investigated in various solvents (Freon 11, chloroform, methanol, trifluoroacetic acid, 2,2,2-trifluoroethanol, water) in order to define the influence of the experimental conditions on the reaction. Experiments have been carried out by varying the temperature, the substrate concentration in solution, the molar ratio of fluorine to substrate, and the concentration of fluorine in the fluorine/nitrogen mixture. In all cases, the effects on the yield of fluorinated products were studied. Monofluorinated compounds were mainly found in the reaction mixture, the isomers formed being in accord with the mechanism for electrophilic substitution. The highest yield of monofluorinated products was obtained with polar solvents and the following order was found: CFCl3 < CHCl3 < CH3OH < CF3CH2OH < CF3COOH. Interesting results were also found using particular additives (for instance, KOH or C4F9SO3Na in methanol) or water as the solvent. A direct relationship was observed between the yield of monofluorinated compounds and the molar ratio of fluorine to substrate, which has to be less than one in order to obtain high yields. In contrast, low selectivity, expressed as the yield ratio of ortho to para (or meta) isomers, was found. 相似文献