Reaction kinetics of carbon dioxide with glycidyl methacrylate using immobilized trioctylamine supported on poly(styrene-CO-vinylbenzyl chloride) as a catalyst

A soluble polymer-supprted catalyst containing pendant trioctylammonium chloride was synthesized by the radical copolymerization of p-chloromethylated styrene with styrene followed by the addition reaction of the resulting copolymer with trioctylamine. Absorption rate of carbon dioxide into glycidyl methacrylate (GMA) solutions containing the catalyst was measured using a semi-batch stirred tank with a plane gas-liquid interface at 101.3 kPa. The reaction kinetics of the reaction between carbon dioxide and GMA was evaluated using the absorption rate and the mass transfer mechanism of carbon dioxide. Solvents such as toluene, N-methyl-2-pyrrolidinone, and dimethyl sulfoxide influenced the reaction rate constants. Furthermore, this catalyst was compared to the monomeric tetraoctylammonium chloride under the same reaction conditions.     

Grafting of polymers onto a carbon‐fiber surface by ligand‐exchange reaction of poly(vinyl ferrocene‐co‐vinyl monomer) with polycondensed aromatic rings of the surface

To improve the surface of carbon fiber, the grafting reaction of copolymer containing vinyl ferrocene (VFE) onto a carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber was investigated. The copolymer containing VFE was prepared by the radical copolymerization of VFE with vinyl monomers, such as methyl methacrylate (MMA) and styrene, using 2,2′‐azobisisobutyronitrile as an initiator. By heating the carbon fiber with poly(VFE‐co‐MMA) (number‐average molecular weight: 2.1 × 10⁴) in the presence of aluminum chloride and aluminum powder, the copolymer was grafted onto the surface. The percentage of grafting reached 46.1%. On the contrary, in the absence of aluminum chloride, no grafting of the copolymer was observed. Therefore, it is considered that the copolymer was grafted onto the carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber. The molar number of grafted polymer chain on the carbon‐fiber surface decreased with increasing molecular weight of poly(VFE‐co‐MMA) because the steric hindrance of grafted copolymer on the carbon‐fiber surface increases with increasing molecular weight of poly(VFE‐co‐MMA). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1868–1875, 2002     

Diphenylprolinol Silyl Ether Catalyzed Asymmetric Michael Reaction of Nitroalkanes and β,β‐Disubstituted α,β‐Unsaturated Aldehydes for the Construction of All‐Carbon Quaternary Stereogenic Centers

The asymmetric Michael reaction of nitroalkanes and β,β‐disubstituted α,β‐unsaturated aldehydes was catalyzed by diphenylprolinol silyl ether to afford 1,4‐addition products with an all‐carbon quaternary stereogenic center with excellent enantioselectivity. The reaction is general for β‐substituents such as β‐aryl and β‐alkyl groups, and both nitromethane and nitroethane can be employed. The addition of nitroethane is considered a synthetic equivalent of the asymmetric Michael reaction of ethyl and acetyl substituents by means of radical denitration and Nef reaction, respectively. The short asymmetric synthesis of (S)‐ethosuximide with a quaternary carbon center was accomplished by using the present asymmetric Michael reaction as the key step. The reaction mechanism that involves the E/Z isomerization of α,β‐unsaturated aldehydes, the retro‐Michael reaction, and the different reactivity between nitromethane and nitroethane is discussed.     

Mechanism of radiation-induced addition reaction of carbon tetrachloride onto liquid 1,2-polybutadiene accompanied by cyclization

Effects of irradiation conditions were investigated in the γ-ray-induced addition reaction of carbon tetrachloride onto liquid 1,2-polybutadiene. The rate of addition reaction was proportional to the dose rate, and its apparent activation energy was 1.4 kcal/mole in the range of ca. 20–80°C; the G values for the addition of carbon tetrachloride and vinyl consumption were high. The addition reactions of methyl isobutylate, isopropyl amine, and bromotrichloromethane to liquid 1,2-polybutadiene by γ rays were studied to compare with carbon tetrachloride. Methyl isobutylate and isopropyl amine were added much more slowly. On the other hand, in bromotrichloromethane the rate of addition reaction was much faster but cyclization was less pronounced than in carbon tetrachloride. On the basis of these results a mechanism of a radical chain reaction which includes the addition of carbon tetrachloride, cyclization, and crosslinking, is proposed.     

Heat-Resistant Polymer-Grafted Carbon Black: Grafting of Poly(Amide-Imide) Onto Carbon Black

Aromatic poly(amide-imide) with terminal isocyanate groups (PAINCO) was prepared by the polycondensation of trimellitic anhydride and a slight excess of 4,4′-diphenylmethane diisocyanate in N-methyl-2-pyrrolidone (NMP) at 160°C for 20 h. PAI was effectively grafted onto the surface by the reaction of PAI-NCO with carbon black: the percentage of grafting onto FW 200 and Neospectra II was determined to be 41.2 and 39.5%, respectively. When the carboxyl and phenolic hydroxyl groups on carbon black were blocked by treatment with diazomethane, the grafting of PAI-NCO onto the treated carbon black does not proceed. Therefore, it is concluded that PAI-NCO reacts with the carboxyl and phenolic hydroxyl groups on carbon black and PAI is grafted through amide and urethane bonds, respectively. The reaction of PAI-NCO with carbon black was accelerated by the addition of amines as catalyst and by raising of the reaction temperature. Thermogravimetric analysis indicated that PAI-grafted carbon black was stable in air up to about 300°C. The PAI-grafted carbon black was found to give a stable colloidal dispersion in NMP.     

Graft Polymerization of Vinyl Monomers Onto Carbon Black by Use of the Redox System Consisting of Ceric Ions and Carbon Black Carrying Alcoholic Hydroxyl Groups

The radical graft polymerization of vinyl monomers onto carbon black initiated by a redox system consisting of ceric ion and carbon black having alcoholic hydroxyl groups was investigated. The introduction of alcoholic hydroxyl groups onto the carbon black surface was achieved by the reaction of carbon black with alcoholic hydroxyl radicals, formed by the reaction of alcohol with benzoyl peroxide. The rate of the polymerization of acrylamide (AAm) initiated by the redox system was found to increase in the following order of hydroxyl groups: 1-hydroxyoctyl < 1-hydroxypropyl < 1-hydroxyethyl < hydroxymethyl < 1-hydroxy-1-methylethyl. In the redox polymerization, poly-AAm was effectively grafted onto carbon black by propagation of the polymer from the radical formed by the reaction of ceric ions with the alcoholic hydroxy groups. The percentage of grafting increased with increasing conversion. By use of this redox system, poly(acrylic acid), polyacrylonitrile, and poly(N-vinyl-2-pyrrolidone) could be grafted onto carbon black, but poly(methyl methacrylate) and polystyrene could not be so grafted. The graft polymerization of AAm by use of a redox system consisting of ceric ion and PVA-grafted carbon black was also investigated.     

Catalytic Activity of Polymetalorganosiloxanes Supported on Silica in the Metathesis of a C–Cl Bond

The catalytic activity of structurally different Cu- and Ni-containing polymetalorganosiloxanes supported on silica was studied using the reaction of C–Cl bond metathesis in the carbon tetrachloride–saturated hydrocarbon (n-decane) system as an example. Catalysts with low metal contents were found to exhibit the highest activity; an increase in the metal content resulted in a decrease in both conversion and specific activity. At the initial portions of kinetic curves, the reaction was described by first-order rate equations with respect to n-decane; the reaction was of fraction order with respect to CCl₄and catalyst. The activation energy of the process in the n-decane–carbon tetrachloride system on a copper-containing network catalyst was 23 ± 2 kcal/mol. The mechanism of catalysis on immobilized catalysts from the above class is discussed.     

Mechanistic Insights into Rhenium-Catalyzed Regioselective C-Alkenylation of Phenols with Internal Alkynes

A (μ-aryloxo)rhenium complex was isolated and confirmed as a key precatalyst for rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes. The reaction exclusively provided ortho-alkenylphenols; the formation of para or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products was not observed. Several mechanistic experiments excluded a classical Friedel–Crafts-type mechanism, leading to the proposed phenolic hydroxyl group assisted electrophilic alkenylation as the most plausible reaction mechanism. For this purpose, the use of rhenium, a metal between the early and late transition metals in the periodic table, was key for the activation of both the soft carbon–carbon triple bond of the alkyne and the hard oxygen atom of the phenol, at the same time. ortho-Selective alkenylation with allenes also provided the corresponding adducts with a substitution pattern different from that obtained by the addition reaction with alkynes.     

Polymerization of vinyl monomer with carbon disulfide–alkali metal complex

The reaction of carbon disulfide with one or two equivalents of alkali metal (potassium- or sodium) was carried out, and the deep red reaction mixture obtained only in diethylene glycol dimethyl ether. The polymerization of vinyl monomers with this reaction mixture was studied. The reaction mixtures of mono- and dialkali metal with carbon disulfide induced the polymerization of N-phenylmaleimide, methyl vinyl ketone, and acrylonitrile but did not induce the polymerization of methyl methacrylate and styrene. In the polymerization of acrylonitrile with this reaction mixture of carbon disulfide with monoalkali metal, the polymerization rate was found to be proportional to the initiator concentration and to the square of the monomer concentration. The activation energy was ?1.1 kcal/mole. Similar results were obtained in the case of carbon disulfide with dialkali metal. The polymer yield increased with increasing solvating power of solvents, i.e., diethylene glycol dimethyl ether, dimethyl sulfoxide, hexamethylphosphoramide, dimethylformamide, tetrahydrofuran. In the copolymerization of AN with MMA, the copolymer obtained consisted almost of AN units.     

Determination of Effective Potentials for Non-polar Liquids Using the Continuum Dielectric Model

Abstract

The “effective potential” for each system, nitrogen, argon, krypton, xenon, methane, benzene, carbon tetrachloride, carbon disulfide, n-hexane and cyclohexane was calculated by using the Clausius-Mossotti, Onsager and Kirkwood reaction fields with Lennard-Jones and Kihara potential parameters assumed. It was found that the Kirkwood reaction field with an assumed Kihara potential is a useful technique to study interactions arising due to physical association and chemical bonding.     

Studies on reactions of the N-phosphonium salts of pyridines. XIII. Direct polycondensation reaction of carbon dioxide or disulfide with diamines under mild conditions

Polyureas of high molecular weight were obtained by the direct polycondensation reaction of carbon dioxide with diamines at 40°C for several hours under a pressure of carbon dioxide (below 30 atm) by use of diphenyl phosphite in pyridine. Optimal temperature and pressure were 40°C and 20 atm of carbon dioxide. The polycondensation reaction was also affected by solvents and type and amounts of tertiary amines. Pyridine was most effective as tertiary amine and solvent as well. Of the phosphorous compounds used, triaryl phosphites and diphenyl phosphite were most effective, but trialkyl phosphites failed to give polymer. The reaction was assumed to proceed via a carbamyl N-phosphonium salt of pyridine formed by dephenoxylation of phosphites. Similarly, polythioureas were prepared by heating a mixture of carbon disulfide, diamines, and diphenyl phosphite in pyridine at 40°C for 6 hr under nitrogen.     

Evaluation of mass-transfer and kinetic parameters forRhodospirillum rubrum in a continuous stirred tank reactor

The photosynthetic bacteriumRhodospirillum rubrum has been evaluated for its ability to produce hydrogen from carbon monoxide and water in a continuous stirred tank reactor according to the watergas shift reaction. An assessment of mass-transfer parameters and reaction kinetics was made for this sparingly soluble substrate system. Experiments were conducted in a nonsteady-state fashion with continuous liquid and gas flow, which allowed for separation of the mass-transfer and kinetic-limited regions. Based on the data obtained, mass-transfer coefficients for the system were determined, and a mathematical expression for the reaction kinetics was formulated. The results showed that the hydrogen production was inhibited by elevated levels of dissolved carbon monoxide in the liquid.     

An Improving Method For the Preparation of Ethynylferrocene

Ethynylferrocene was prepared in satisfactory yield by reaction of formylferrocene with triphenylphosphine and carbon tetrachloride followed by dehydrohalogenation in presence of n-butyllithum. The reaction condition is mild and the reaction time is much shorter. The method is convenient and economical.     

Rhenium-Catalyzed Construction of Polycyclic Hydrocarbon Frameworks by a Unique Cyclization of 1,n-Diynes Initiated by 1,1-Difunctionalization with Carbon Nucleophiles

A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon–carbon bonds in a single step. The reaction proceeds under neutral conditions and does not require external ligands or additives. The key to this reactivity is the unique activation mode of the rhenium carbonyl complex, which prefers to interact with heteroatoms in polar carbon–heteroatom bonds as well as nonpolar carbon–carbon unsaturated π bonds.     

A new synthetic route to 7H-imidazo[1,2-b][1,2,4]triazoles

The reaction of benzil 1-ureidoethylidenehydrazones 8 with a mixture of triphenylphosphine, carbon tetrachloride, and triethylamine provides a general route to 7H-imidazo[1,2-b][1,2,4]triazoles 18 via the thermal reaction of the expected ketoazine carbodiimide intermediates 13 , and the structure of 18 was confirmed by X-ray crystallographic analysis.     

Electrochemical-Induced Ring Transformation of Cyclic α-(ortho-Iodophenyl)-β-oxoesters

Cyclic α-(ortho-iodophenyl)-β-oxoesters were converted in a ring-expanding transformation to furnish benzannulated cycloalkanone carboxylic esters. The reaction sequence started by electrochemical reduction of the iodoarene moiety. In a mechanistic rationale, the resulting carbanionic species was adding to the carbonyl group under formation of a strained, tricyclic benzocyclobutene intermediate, which underwent carbon–carbon bond cleavage and rearrangement of the carbon skeleton by retro-aldol reaction. The scope of the reaction sequence was investigated by converting cyclic oxoesters with different ring sizes yielding benzocycloheptanone, -nonanone and -decanone derivatives in moderate to good yields. Furthermore, acyclic starting materials and cyclic compounds carrying additional substituents on the iodophenyl ring were submitted to this reaction sequence. The starting materials for this transformation are straightforwardly obtained by conversion of β-oxoesters with phenyliodobis(trifluoroacetate).     

Rhodium‐Catalyzed Cascade Reaction of 1,6‐Enynes Involving Addition,Cyclization, and β‐Oxygen Elimination

The reaction of arylboronic acids with 1,6‐enynes that contain an allylic ether moiety is catalyzed by a rhodium(I) complex to produce cyclopentanes with a tetrasubstituted exo olefin and a pendant vinyl group. The reaction is initiated by the regioselective addition of an arylrhodium(I) species to the carbon–carbon triple bond of the 1,6‐enyne. The resulting alkenylrhodium(I) compound subsequently undergoes intramolecular carborhodation of the allylic double bond in a 5‐exo‐trig mode. β Elimination of the methoxy group affords the cyclization product and the catalytically active methoxorhodium(I) species. The use of alkyl Grignard reagents instead of arylboronic acids as organometallic nucleophiles was also examined.     

Carbon black/alumina gel composite: Preparation by sol-gel process in the presence of polymer-grafted carbon black and its electric properties

The preparation of a novel carbon black/alumina gel composite by sol-gel reaction of aluminum isopropoxide (AIP) was investigated. When sol-gel reaction of AIP was carried out in the presence of untreated carbon black, a thin film of alumina gel was hardly obtained, because of the presence of aggregated carbon blacks. On the contrary, in the presence of poly(N-vinyl-2-pyrrolidone)-grafted, poly(2-methyl-2-oxazoline)-grafted, and poly(N,N-diethylacrylamide)-grafted carbon black, a deep-black, thin film of alumina gel, in which carbon blacks were uniformly incorporated, was obtained. Carbon black was incorporated into an alumina gel matrix by the hydrogen bond between carbonyl groups of the grafted polymer and the residual hydroxyl groups in the alumina gel. Electric resistance of the polymer-grafted carbon black/alumina gel composite was very sensitive to the vapor of solvents of the grafted polymer chains on carbon black surface: the electric resistance of the composite drastically decreased in humidity and N,N-dimethylformamide vapor, but not in n-hexane vapor. The logarithm of electric resistance of polymer-grafted carbon black/alumina gel composite linearly decreased in proportion to relative humidity. In addition, the electric resistance of poly(N,N-diethylacrylamide)-grafted carbon black/alumina gel composite under humidity decreased drastically at 32°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3591–3597, 1999     

A new synthetic route to 7H-imidazo[1,2-b][1,2,4]triazoles

The reaction of benzil 1-ureidoethylidene hydrazones 8 with a mixture of triphenylphosphine, carbon tetrachloride, and triethylamine provides a general route to 7H-imidazo[1,2-b][1,2,4]triazoles 18 via the thermal reaction of the expected keto azine carbodiimide intermediates 13, and the structure of 18 was confirmed by X-ray crystallographic analysis.