Pressure thiophene

Trimethylamine, azeotrope composition independent of pressure Thiophene Crotonaldehyde... 

Pd(II) salts promote the carbonylation of organomercury compounds. Reaction of phenylmercury chloride and PdCh under CO pressure affords benzophenone (429)[387]. Both esters and ketones are obtained by the carbonylation of furylmercury(Il) chloride in alcohol[388]. Although the yields are not satisfactory, esters are obtained by the carbonylation of aryl- and alkylmercuryfll) chlorides[389,390]. One-pot catalytic carbonylation of thiophene, furan, and pyrrole (430) takes place at the 2-position via mercuration and transmetallation by the use of PdCb, Hg(N03), and CuCl2[391]. 

Examples of the hydroquinone inclusion compounds (91,93) are those formed with HCl, H2S, SO2, CH OH, HCOOH, CH CN (but not with C2H 0H, CH COOH or any other nitrile), benzene, thiophene, CH, noble gases, and other substances that can fit and remain inside the 0.4 nm cavities of the host crystals. That is, clathration of hydroquinone is essentially physical in nature, not chemical. A less than stoichiometric ratio of the guest may result, indicating that not all void spaces are occupied during formation of the framework. Hydroquinone clathrates are very stable at atmospheric pressure and room temperature. Thermodynamic studies suggest them to be entropic in nature (88). 

Endo adducts are usually favored by iateractions between the double bonds of the diene and the carbonyl groups of the dienophile. As was mentioned ia the section on alkylation, the reaction of pyrrole compounds and maleic anhydride results ia a substitution at the 2-position of the pyrrole ring (34,44). Thiophene [110-02-1] forms a cycloaddition adduct with maleic anhydride but only under severe pressures and around 100°C (45). Addition of electron-withdrawiag substituents about the double bond of maleic anhydride increases rates of cycloaddition. Both a-(carbomethoxy)maleic anhydride [69327-00-0] and a-(phenylsulfonyl) maleic anhydride [120789-76-6] react with 1,3-dienes, styrenes, and vinyl ethers much faster than tetracyanoethylene [670-54-2] (46). 

Process Description. Reactors used in the vapor-phase synthesis of thiophene and aLkylthiophenes are all multitubular, fixed-bed catalytic reactors operating at atmospheric pressure, or up to 10 kPa and with hot-air circulation on the shell, or salt bath heating, maintaining reaction temperatures in the range of 400—500°C. The feedstocks, in the appropriate molar ratio, are vaporized and passed through the catalyst bed. Condensation gives the cmde product mixture noncondensable vapors are vented to the incinerator. 

Thiophene fails to undergo cycloaddition reactions with common dienophiles under normal conditions. However, when thiophene is heated under pressure with maleic anhydride, the exo adduct (136) is formed in moderate yield (78JOC1471). 

Example 7 Estimate the Vapor Pressure of Thiophene at 500 K.. . . Example 8 Estimate the Vapor Pressure of Acetaldehyde at 0 C. . . Ideal Gas Thermal Properties. 

The main product, benzene, is represented by solute (B), and the high boiling aromatics are represented by solute (C) (toluene and xylenes). The analysis of the products they obtained are shown in Figure 12. The material stripped form the top section (section (1)) is seen to contain the alkanes, alkenes and naphthenes and very little benzene. The product stripped from the center section appears to be virtually pure benzene. The product from section (3) contained toluene, the xylenes and thiophen which elutes close to benzene. The thiophen, however, was only eliminated at the expense of some loss of benzene to the lower stripping section. Although the system works well it proved experimentally difficult to set up and maintain under constant operating conditions. The problems arose largely from the need to adjust the pressures that must prevent cross-flow. The system as described would be virtually impossible to operate with a liquid mobile phase. 

Although desulfurization is a process, which has been in use in the oil industry for many years, renewed research has recently been started, aimed at improving the efficiency of the process. Envii onmental pressure and legislation to further reduce Sulfur levels in the various fuels has forced process development to place an increased emphasis on hydrodesulfurization (HDS). For a clear comprehension of the process kinetics involved in HDS, a detailed analyses of all the organosulfur compounds clarifying the desulfurization chemistry is a prerequisite. The reactivities of the Sulfur-containing structures present in middle distillates decrease sharply in the sequence thiols sulfides thiophenes benzothiophenes dibenzothio-phenes (32). However, in addition, within the various families the reactivities of the Substituted species are different. 

Keywords furans, pyrroles, thiophenes, phospholes, oxazoles, pyrones, pyr-idones, oxazinones, high pressure... 

The first example of microwave-promoted solid-phase methodology in heterocyclic chemistry was the arylation of thiophene and indole via Suzuki couplings on TentaGel S RAM resin, as demonstrated by Hallberg and coworkers in 1996, before temperature- and pressure-controlled microwave instruments were even available [189]. Three years later Schotten and coworkers presented analogous but aqueous Suzuki couplings of 5-bromo-thiophene anchored to PEG soluble support via a carboxylic function at its C-2 position [116]. Unfortunately, this work was performed in a do-... 

Figure 7.16. Dependence of the rate of thiophene hydrodesulfurization on the partial pressures of the reactants thiophene and hydrogen and of the product hydrogen sulfide,...

Figure 7.18. Dependence of the rate of thiophene hydrodesulfurization on the partial pressures of thiophene at different temperatures, along with fits according to the Langmuir-Hinshelwood model, Eq. (32). [Fron A. Borgna and J.W. Niemantsverdriet, to be published (2003).]...

Where pr is the partial pressure of thiophene and is the partial pressure of hydrogen. 

Kinetics over the Mo(lOO) Crystal Surface. We have studied the hydrodesulfurization of thiophene over the initially clean Mo(lOO) single crystal surface in the temperature range 520K - 690K and at reactant pressures of 100 Torr < P(H ) 800 Torr and 0.1 Torr P(Th) < 10 Torr. Under these conditions the reaction is catalyzed at a constant rate for a period of approximately one hour after which the rate begins to decrease with time. The rates reported here are all initial rates of reaction calculated from data collected in the period over which they remain constant. 

The studies of ammonia synthesis over Fe and Re and the hydrodesulfurization of thiophene over Mo, described above, illustrate the importance and success of our approach of studying catalysis over single crystal samples at high pressures. The use of surfaces having a variety of orientations allows the study of reactions that are surface structure sensitive 6Uid provides insight into the nature of the catalytic site. Here we have shown that the ammonia synthesis... 

Atkinson R, SM Aschmann, AM Winer, WPL Carter (1985b) Rate constants for the gas-phase reactions of NOj radicals with furan, thiophene, and pyrrole at 295 1 K and atmospheric pressure. Environ Sci Technol 19 87-90. 

The sulfided catalysts were evacuated for 1 h before catalytic reactions. The reactions were carried out under mild conditions by using a circulation system (0.2 dm ) made of glass. The HDS of thiophene was conducted at 623 K and an initial pressure of 20 kPa (Hj/C H, = 36). The thiophene pressure was kept constant (0.54 kPa) during the reaction by holding a small amount of liquid thiophene kept at 273 K in the bottom of a U-tube in the reaction system. The products were analyzed by gas chromatography. The HDS activity was calculated from the amount of H S produced during the reaction. 

The hydrogenation (HYD) of butadiene was subsequently conducted at 473 K over the catalyst, that had been used for the HDS of thiophene for 1 h, after evacuation at 673 K for 1 h. The initial pressure was 14 kPa (HJ/C4H4 = 2). The HYD products were butenes with a small amount of butane. The catalytic activity was calculated on the basis of the total amount of the reaction products. 

The combined information gathered from kinetic studies,184 in situ high-pressure NMR experiments,184,185,195 and the isolation of intermediates related to catalysis, leads to a common mechanism for all the hydrogenolysis reactions of (102)-(104) and other thiophenes catalyzed by triphos- or SULPHOS-rhodium complexes in conjuction with strong Bronsted bases. This mechanism (Scheme 41) involves the usual steps of C—S insertion, hydrogenation of the C—S inserted thiophene to the corresponding thiolate, and base-assisted reductive elimination of the thiol to complete the cycle.184 185 195-198... 

Ti-Beta catalyst was synthesized according to reference [8], Thiophene and model compound oxidation were carried out at 8O0C in a block heater with magnetic stirring (500 rpm) in multiple high pressure tubes. Individual samples were prepared of 0.1 mol 30 % H202 solution, 0.02 mol thiophene, 25 g heptane and 100 mg Ti-Beta catalyst were added at room temperature,, and heated to 80°C. The same oxidation conditions were also investigated without heptane solvent. The reaction was stopped at different... 

An alternative, rather esoteric direct thiophene synthesis is illustrated in Scheme 83, in which a structurally novel149 thiaphosphanorbornadiene complex (67) is pyrolyzed under a pressure of carbon monoxide.150... 

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