Palladium-catalyzed addition reaction of olefins,carbon tetrachloride and carbon monoxide in alcohols to give 2-alkyl-4,4,4-trichlorobutanoates

Pd(OAc)₂ combined with PPh₃ is a good catalyst for the addition reaction of CCl₄ and CO to olefins in ethanol to afford ethyl 2-alkyl-4,4,4-trichlorobutanoates. The esters were obtained in satisfactory yields when the reaction was carried out at 50° in the presence of K₂CO₃ under CO pressure.     

Palladium-catalysed oxidation of alcohols with carbon tetrachloride,formation of 4,4,4-trichloro ketones from allylic alcohols and carbon tetrachlorid

Pd salts catalyse oxidation of alcohols with CCl₄ in the presence of K₂CO₃. Primary alcohols are oxidised to esters, and secondary alcohols to ketones. CCl₄ is converted to CHCl₃. The reaction of allylic alcohols bearing a terminal olefinic bond with CCl₄ or BrCCl₃ in the presence of palladium catalyst at 110° affords 4,4,4-trichloro ketones. At 40°, simple adducts of CCl₄ or BrCCl₃ having a halohydrin structure are obtained, which are converted to the corresponding trichloro ketones by the catalysis of palladium. Various halohydrins are converted to ketones by Pd catalysis.     

Efficient One-Pot Synthesis of 2-Chloro-1,1, 1-trifluoro-2-alkenes Under Solvent-Free Conditions

The improved one-pot Wittig reaction had been used to prepare trifluoromethyl-containing olefins under solvent-free conditions. Treatment of aldehydes with PPh₃ and CF₃CCl₃ in the presence of K₂CO₃ at 100 °C afforded 2-chloro-1,1,1-trifluoro-2-alkenes in good to moderate yields.     

Addition of CCl4 to unsaturated compounds catalyzed by M3(CO)12 (M=Fe, Ru, Os)

The addition of CCl₄ to hex-1-ene and to the methyl ester ofN-(trans-cinnamoyl)-l-proline (2) catalyzed by M₃(CO)₁₂ or by the M₃(CO)₁₂+DMF system (M=Fe, Ru, Os) was studied. The use of ruthenium and osmium dodecacarbonyls in combination with DMF increases the yields of adducts CCl₃CH₂CHClC₄H₉ (4) and PhCHClCH(CCl₃)C(O)R′ (3) over those obtained in reactions catalyzed by the same carbonyls without DMF. In addition to adduct3, salts [M(CO₃)Cl₃]⁻[Me₂NH₂]⁺ were isolated from the products of the reaction between CCl₄ and1 in the presence of M₃(CO)₁₂+DMF (M=Ru, Os). These salts do not catalyze this reaction and apparently result from chain termination. Experimental results in favor of a coordination mechanism of the addition of CCl₄ to olefins in the presence of Ru₃(CO)₁₂ and Os₃(CO)₁₂ were obtained. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 6, pp. 1174–1179, June, 1997.     

Reaction of α,α,ω-trichloro- and α,α,α,ω-tetrachloroalkanes with alkali metal acylates in aprotic solvents

Polychloroalkanes and -alkenes R(CH₂)_nCl (R=CHCl₂CH₂, CCl₂=CH, n=1, 3) in dipolar aprotic solvents — dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphoramide (HMPA) — at 130–150°C react selectively at the CH₂Cl group with salts of carboxylic acids RCO₂K(Na) to form dichloroesters RCO₂· (CH₂)_nR (R=CHCl₂CH₂, CCl₂=CH). In tetrachloroalkanes CCl₃CH₂(CH₂)_nCl (n = 1, 3, 5) under the same conditions the selectivity of the CCl₃ and CH₂Cl groups relative to the nucleophile RCO₂K(Na) is altered — unsaturated esters RCO₂(CH₂)_nCH=CCl₂ are formed in one stage with yields of 75–90%. Under the selected conditions, high conversion of polychloroalkanes to esters is attained 3 to 5 times more rapidly than in acid media. The structure of the ester obtained has been confirmed by their PMR spectra.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2790–2793, December, 1990.     

PdCl2(MeCN)2-catalyzed carbonylation of diethylamine with carbon dioxide: Selective synthesis of tetraethylurea and diethylformamide

The reaction of diethylamine with carbon dioxide (CO₂) with PdCl₂(MeCN)₂ as a catalyst gives tetraethylurea(1) or diethylformamide(2) selectively under mild reaction conditions by employing the PPh₃/CCl₄/MeCN and the HCOONa/methyl cellosolve systems, respectively.     

NMR studies on the stereospecific polymerization of methyl vinyl ether. Part I. Polymerization by metal halides: Penultimate effect

Methyl vinyl ether (MVE) was polymerized under various conditions by BF₃·O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H catalysts. The effect of polymerization conditions on the steric structure of poly(methyl vinyl ether) (PMVE) was studied by NMR spectra. It was found that the triad isotacticity of PMVE decreased and the syndiotacticity and heterotacticity increased with increasing polarity of the solvent and increasing polymerization temperature. This result coincided with the qualitative conclusion estimated from softening point and infrared spectra. However, the variation of tacticity by the change of the polarity of a solvent was not so large as expected. There was no large difference between the behavior of BF₃·O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H as catalysts. From the relation between the difference of free energy of monomer addition due to the steric structure of the polymer and the polymerization temperature, it was concluded that the penultimate effect really existed and was due to only the difference in enthalpy in the MVE–BF₃. O(C₂H₅)₂ or MVE–SnCl₄·CCl₃CO₂H systems. The penultimate effect was not greatly changed by the polymerization conditions in these systems.     

Electrocarboxylation of Carbon Tetrachloride in Dimethylformamide with Use of a Soluble Zinc Anode

Regularities of electrochemical carboxylation of carbon tetrachloride in conditions of galvanostatic diaphragmless electrolysis with a soluble zinc anode are studied. It is established that the generation of the CCl ₃ ^? anion at the cathode is accompanied by the discharge of salts of Zn²⁺, with the deposition of Zn⁰ at the surface. The interaction between and CCl ₃ ^? and CO₂ in experimental conditions leads to the formation of zinc trichloromethylacetate, which proves to be very unstable in the dimethylformamide environment and undergoes fragmentation with the CO₂ evolution. It is found that this process competes with currentless reduction of trichloromethylacetate under the action of Zn⁰ deposited on the cathode surface. As a result, corresponding dichloromethylacetate with a small yield of ≤5.5% forms as the sole product of electrolysis.     

Telomeres photoreticulables—3. Synthèse de telomeres photoreticulables a partir du cinnamate d'allyle et de l'acetate d'allyle

Photocrosslinkable telomers cannot be prepared by the direct telomerisation of allyl cinnamate. However, such materials can be prepared by reaction of cinnamoyl chloride with hydrolysed telomers of allyl acetate. Transfer constants of the three telogens, (H-P(0)(OEt)₂, CCl₂HCO₂CH₃ and CCl₃CO₂CH₃) towards allyl acetate were determined also.     

Evidence for Ps formation in spurs in high-density gaseous CO2

Measurements of Ps yields in mixtures of CO₂ and Ar with the electron scavengers CCl₄ and CCl₂F₂ are reported. It is shown that the CO₂ mixtures provide direct evidence for Ps formation in spurs in this gas. Further, some support is also given to recent models which consider Ps formation in gases by both Ore and spur processes. The results obtained for the Ar mixtures are consistent with the Ore model of Ps formation.     

Direct Oxidative Coupling of Arenes with Olefins by Rh‐Catalyzed C?H Activation in Air: Observation of a Strong Cooperation of the Acid

A [{RhCl(cod)}₂]/CCl₃COOH system was developed for the oxidative coupling of non‐chelate‐assisted arenes with olefins in the presence of catalytic amounts of Cu(OAc)₂ ? H₂O as a co‐oxidant and oxygen as the terminal oxidant. The acid was an indispensable component in this system and played a very important role in the coupling reaction. This catalytic system was applied to the direct oxidative coupling of a series of arenes and olefins and the corresponding products were afforded in high yields with special chemo‐ and regioselectivity. This reaction provides an atom‐efficient route to vinylarenes, which are widely used in various fine chemicals.     

Reaction Mechanisms in Both a CCl2F2/O2/Ar and a CCl2F2/H2/Ar RF Plasma Environment

Decomposition of dichlorodifluoromethane (CCl₂F₂ or CFC-12) in aradiofrequency (RF) plasma system is demonstrated. The CCl₂F₂decomposition fractions _{CCl 2 F 2} and mole fractionsof detected products in the effluent gas stream of CCl₂F₂/O₂/Ar andCCl₂F₂/H₂/Ar plasma, respectively, have been determined. The experimentalparameters including input power wattage, O₂/CCl₂F₂ or H₂/CCl₂F₂ ratio,operational pressure, and CCl₂F₂ feeding concentration wereinvestigated. The main carbonaceous product in the CCl₂F₂/O₂/Arplasma system was CO₂, while that in the CCl₂F₂/H₂/Ar plasma systemwas CH₄ and C₂H₂. Furthermore, the possible reaction pathways werebuilt-up and elucidated in this study. The results of the experimentsshowed that the highly electronegative chlorine and fluorine wouldeasily separate from the CCl₂F₂ molecule and combine with the addedreaction gas. This led to the reactions terminated with the CO₂,CH₄, and C₂H₂ formation, because of their high bonding strength. Theaddition of hydrogen would form a preferential pathway for the HCland HF formations, which were thermodynamically stable diatomicspecies that would limit the production of CCl₃F, CClF₃, CF₄, andCCl₄. In addition, the HCl and HF could be removed by neutral orscrubber method. Hence, a hydrogen-based RF plasma system provideda better alternative to decompose CCl₂F₂.     

Kinetics of Oxidative Cracking of n-Hexane to Light Olefins using Lattice Oxygen of a VOx/SrO-γAl2O3 Catalyst

The kinetics of oxidative cracking of n-hexane to light olefins using the lattice oxygen of VO_x/SrO-γAl₂O₃ catalysts has been investigated. Kinetic experiments were conducted in a CREC Riser Simulator (CERC: Chemical Reactor Engineering Center), which mimics fluidized bed reactors. The catalyst's performance is partly attributed to the moderate interaction between active VO_x species and the SrO-γAl₂O₃ support. This moderate interaction serves to control the release of lattice oxygen to curtail deep oxidation. The incorporation of basic SrO component in the support also helped to moderate the catalyst's acidity to checkmate excessive cracking. Langmuir-Hinshelwood model was applied to formulate the rate equations. The intrinsic kinetic parameters were obtained by fitting the experimental data to the kinetic model using a nonlinear regression algorithm at a 95% confidence interval, implemented in MATLAB. n-Hexane transforms to olefins at a specific reaction rate of 1.33 mol/gcat.s and activation energy of 119.2 kJ/mol. These values when compared with other duplets (i. e., ki° and E_A) for paraffins to olefins, show that indeed olefins are stable products of the oxidative conversion of n-hexane over VO_x/SrO-γAl₂O₃ under a fluidized bed condition. Values of activation energy for all CO_x formation routes indicate that intermediate paraffins are likely to be cracked to form CH₄ than to be converted directly to CO_x. On the other hand, olefins may transform partly, and directly to CO_x (E₉=9.65 kJ/mol) than to form CH₄ (E₈=89.1 kJ/mol) in the presence of excess lattice oxygen. Overall, olefins appear to be stable to deep oxidation due to the role of SrO in controlling the amount of lattice oxygen of the catalyst at the reaction temperature.     

Rhodium‐Complex‐Catalyzed Hydroformylation of Olefins with CO2 and Hydrosilane

A rhodium‐catalyzed one‐pot hydroformylation of olefins with CO₂ , hydrosilane, and H₂ has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO₂ reduction to CO and a conventional rhodium‐catalyzed hydroformylation with CO/H₂. The hydrosilylane‐mediated reduction of CO₂ in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.     

Thermal and other properties of complexes of Mn(II), Co(II) and Ni(II) with 2,2'-bipyridine and trichloroacetates

Complexes of the general formulae Mn(2-bpy)₂(CCl₃COO)₂, Co(2-bpy)₂(CCl₃COO)₂·H₂O and Ni(2-bpy)₂(CCl₃COO)₂·2H₂O (where: 2-bpy=2,2'-bipyridine) have been prepared and characterized by VIS and IR spectroscopy, conductivity and magnetic measurements. The thermal properties of complexes in the solid state were studied under non-isothermal conditions in air atmosphere. During heating the complexes decompose via different intermediate products to the oxides Mn₃O₄, CoO and NiO. A coupled TG-MS system was used to detection the principal volatile products of thermal decomposition and fragmentation processes of obtained compounds. The principal volatile products of thermal decomposition of complexes are: H₂O⁺, CO₂ ⁺, Cl₂ ⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fluoration de telomeres polyhalogenes par le fluorure de potassium (2ème partie). Synthese d'olefines perfluorees de hauts poids moleculaires

Fluorination of chlorofluorinated telomers of general formula Cl(CFClCF₂)_nCCl₃ (n ? 7) was studied using potassium fluoride in dimethylsulfoxide as fluorinating agent. The reaction leads to a mixture of perfluorinated linear olefins having 15 to 30 carbon atoms : CF₃(CF₂)_pCFCF(CF₂)_mCF₃ (p + m = 2n?3).We perfected a method to determine molecular weights of the telomers by gel permeation chromatography (G.P.C.). The olefins obtained by fluorination are analyzed both by vapor phase chromatography (V.P.C.) and by ¹⁹F nuclear magnetic resonance (N.M.R.).     

Transition metal-mediated or catalyzed hydrocarboxylation of olefins with CO2

The development of new methods to incorporate carbon dioxide into organic molecules is of special significance and interest as it is an abundantly available and recyclable C1 source. Catalytic hydrocarboxylation of readily available olefins with CO₂ represents a highly atom- and step-economic approach toward transformations of CO₂ into widely-used aliphatic acids. However, due to relatively lower reactivity of them, this goal has been always a formidable challenge. Herein we review relevant progress on transition metal-mediated or catalyzed methodologies toward the desired hydrocarboxylation, with an emphasis on the development of two main pathways, including transition-metal-catalyzed cyclometallation of olefin and CO₂ and direct addition of alkylmetal to CO₂.     

Cationic polymerization of α,β-disubstituted olefins. XV. Stereospecific polymerization of butenyl ethers by cationic catalysts

Methyl, ethyl, and isopropyl butenyl ethers, CH₃CH₂CH?CHOR, were polymerized with homogeneous catalysts at ?78°C. Toluene, methylene chloride, and nitroethane were used as solvents, and BF₃O(C₂H₅)₂ and SnCl₄·CCl₃CO₂H were used as catalysts. The stereoregularity of the polymers were compared by x-ray diagrams and infrared absorption ratios. The stereoregularity of polymers increased with increasing content of the trans isomer in the monomer and with increasing polarity of the solvent. In the polymerization of methyl and ethyl butenyl ethers, crystalline polymers were obtained from both the trans and cis isomers. The crystalline polymer prepared from the trans isomer and that from the cis isomer had the same steric structure. This behavior is quite different from that observed in the polymerization of propenyl ethers. It is concluded that the bulkiness of the group on the olefinic β-carbon plays an important role in the stereospecific polymerization of α,β-disubstituted olefins.     

Iron(III) nitrate-induced aerobic and catalytic oxidative cleavage of olefins

Microwave-assisted catalytic oxidative cleavage of olefins using Fe(NO₃)₃·9H₂O under O₂ is reported. This reaction system is particularly effective when 9-benzylidene-9H-fluorene derivatives are used as substrates even though they are tri- and tetra-substituted olefins.     

Electrocarboxylation of CCI<Subscript>4</Subscript> in MeCN during electrolysis with the sacrificial Zn anode

The regularities of galvanostatic electrocarboxylation of CCl₄ in Alk₄NBr/MeCN in an undivided cell with sacrificial Zn anode were studied. The major product of the electrolysis is zinc trichloroacetate, which is formed as a result of the reaction of the cathode-generated CCl₃- anion with CO₂. The further trichloroacetate reduction is prevented by cathode passivation. Therefore, small amounts of zinc dichloro- and monochloroacetates are formed due to the chemical reduction of zinc trichloroacetate with Zn⁰ rather than the cathodic reduction. Zero-valence zinc is formed in minor amounts when Zn²⁺ ions are discharged at the cathode surface because of the low solubility of ZnBr₂ in MeCN. The treatment of (Cl₃CCOO)₂Zn with H₂SO₄ in MeOH gives Cl₃CCO₂Me in 11% yield based on the starting CCl₄.