Toluene reaction

Acylation of 3-arylamino-4-arylimino-4//-pyrido[l,2-u]pyrazines (373) with acyl chlorides afforded mixtures of mono- and bisacylated derivatives 374 and 375 (99JPR332). Acetyl chloride gave only monoacylated product 374 (R = 4-MePh, R =Me). Bis-acylated derivative 375 (R = 4-MePh, r = Me) was obtained in 68% yield in boiling toluene. Reaction of 373 with dienophiles 376 and 377 gave 4-thiono and 4-seleno derivatives of 4//-pyrido[l,2-u]pyrazines 378 (Y==S, Se) and 4-imino-4//-pyrido[l,2-u]pyrazines 379, respectively (99JPR332). 

Figure 13. Carbonylation of 2-iodobenzyl alcohol catalyzed by PdCljlPfOCjHslsb in scC02 and in toluene. Reaction conditions S/C = 5000, Pd cat 1,0x 10"2 M DMF solution, Pco =...

Toluenedithiol (Dithiol) molecular formula, 5 712t Toluene reactions... 

Reactions using [Rh(CO)2Cl]2 were run in toluene. Reactions using [Ir(COD)Cl]2 or [Rh(COD)Cl]2 were run in DCE. Amount of additive used was twice the molar amount of catalyst. 75-90% yields for all entries were obtained. Ratios determined by H NMR. 

For example, Klotz et al. (1997, 1998) have shown that benzene oxide/oxepin photolyzes in sunlight to give phenol with a yield of 43.2 + 4.5%. This reaction mechanism is therefore feasible for the formation of phenol in the benzene-OH reaction. However, photolysis of toluene l,2-oxide/2-methyloxepin gave o-cresol only in small yields, 2.7 + 2.2% (Klotz et al., 1998) this suggests that cresols formed in the OH-toluene reaction come primarily from the direct reaction (63) of the OH adduct with 02, in contrast to the conclusions of Moschonas et al. (1999). 

Reaction Vazo Vazo THF Toluene Reaction Yield... 

Mendez-Roman and Cardona-Martinez [55] examined titanium dioxide catalysts with FTIR spectroscopy during the photocatalytic oxidation of toluene. Reaction intermediates, believed to be benzaldehyde and benzoic acid, were reported to accumulate on catalyst samples. This accumulation of intermediates was found to be reduced in the presence of gas-phase water. Mendez-Roman and Cardona-Martinez concluded that toluene appeared to be converted to benzaldehyde, which was then oxidized further to form benzoic acid. They suggested that the accumulation of benzoic acid led to the observed apparent catalyst deactivation. Other researchers, however, have argued that benzoic acid is unlikely to be the compound responsible for apparent deactivation in the photocatalytic oxidation of aromatics. For example, Larson and Falconer [43] concluded, based on higher CO2 evolution rates for benzoic acid relative to toluene during photooxidation, that benzoic acid was not sufficiently recalcitrant to be responsible for the deactivation seen with aromatic contaminants. 

Furosemide can also be synthesized starting with 2,4-dichlorobenzoic acid (formed by chlorination and oxidation of toluene). Reaction with chlorosulfonic acid is an electrophilic aromatic substitution via the species -S02C1 attacking ortho and para to the chlorines and meta to the carboxy-late. Ammonolysis to the sulfonamide is followed by nucleophilic aromatic substitution of the less hindered chlorine by furfurylamine (obtained from furfural—a product obtained by the hydrolysis of carbohydrates). 

There are several kinetic and product studies on Cl atom gas phase reactions of hydrocarbons [16-42], Though the various kinetic studies show more consistency on Cl-I-toluene reaction rates [41], the reactions of Cl- -benzene has been shown to be quite contradictory. Indeed, six existing published studies on the Cl -l- benzene reaction rates vary by more than 5 orders of magnitudes, ranging from 1.3 x 10 to 1.5 X 10 cmV(molecules) [16,17,19,24,27,42],... 

Schleyer proposed one last alternative method for ganging ASE. Noting that many of these better methods (especially those analogons to Reaction 3.24) require computation of many compounds, he developed the isomerization stabilization energy (ISE) method, particularly useful for strained aromatic systems. ISE measures the energy realized when an isomeric compound converts into its aromatic analog. Benzene itself cannot be analyzed by the ISE method, however, toluene can, and the ASE values of toluene and benzene are expected to be quite similar. The conversions of two different isomers into toluene provide the ISE for toluene (Reactions 3.27a and 3.27b). Both of these reactions do not conserve s-cis/s-trans diene conformations. Reaction 3.28 can be added once to Reaction 3.27a and twice to Reaction 3.27b to give the corrected ISE values of -32.0 and -28.9 kcal mol , respectively. 

Materials. Trimethylsilylmethyl methacrylate (Sl) and chloro-methylstyrene (CMS) (mixed m,p isomers) were obtained from Petrarch Systems Inc. and Dow Chemical Co. Inc., respectively. Both monomers were purified by distillation at reduced pressure. Copolymers were prepared by free-radical solution polymerization at 85 C in toluene. Reactions were initiated using benzoyl peroxide. 

Multinuclear Li and NMR and quantum-chemical investigations by Muller and coworkers showed that it is possible to determine the structure of active species in methacrylate polymerization in the presence of triethylaluminum (AlEts) in nonpolar solvents, such as toluene. Reaction of eibLi and trialkylaluminum with methyl pivalate (mpiv), in equimolar amounts, leads to an equilibrium of monomer 46 and dimer 47 complexes (eibLi mpiV"AlEt3) (n = 1, 2), consistent with kinetic studies. Methyl pivalate was... 

Most commercially available methylaluminoxanes are produced by careful reaction of water with trimethylaluminum (TMAL) in toluene. Reaction must be closely controlled to avoid what renowned organometallic chemist John Eisch called "a life threatening pyrotechnic spectacle" (16). Unfortunately, there have been explosions and injuries reported during MAO preparations. Water must be introduced at low temperature and in forms that moderate the potentially violent reaction. For example, water has been introduced as hydrated salts, ice shavings or atomized spray. Even with these precautions, explosive reactions have occurred. The overall reaction is given in eq 6.1. 

C. Aromatic Hydrocarbons, Steam Dealkylation.—Research on steam dealkylation has thrown light on the mechanism of reforming. Rabinovich and other Russian workers, following their earlier research in this area which is summarized by Grenoble, concluded that the toluene reaction with steam over precious metal/alumina catalysts proceeds by simultaneous-consecutive reactions ... 

These cyclopropenone acetals are particularly stable in benzene and toluene. Reaction via the TT-delocalized singlet vinylcarbene proceeded regioselectively with an efficient rate at 70-80°C (see Houben-Weyl, Vol. E19b, Table 109). 

The iron vapor-toluene reaction has evoked interest because of the lability of the proposed bis(arene)iron complex to ligand subsitu-tion and to loss of both toluene molecules to free the metal atom. In the latter case the toluene molecules may be usefully regarded as metal atom carriers which can be used to direct the latent reactivity of the atom in subsequent solution phase chemistry. In this way the metal atom experiment can benefit from the convenience and additional versatility afforded by bench-top chemical manipulations. These results are relevant to a reported preparation of a dehydroxy-lated silica-supported Fischer-Tropsch catalyst from a static reactor codeposition of Fe and toluene.(46) In the liquid phase, iron atoms "bottled" in this way have also been utilized in an exceedingly mild method for making minute catalytically active superparamagnetic clusters on the surface and within the cavities of a dehydrated sodium zeolite Y.(38) Using the rotary reactor, preformed solutions of solvated iron atoms (as the toluene complex) are cannulated below their decomposition temperature out of the flask to a cold slurry of the support in toluene. Diffusion of intact... 

However, experiments have shown that toluene-d8 (completely substituted with deuterium) gives exactly the same smog chamber behavior as toluene itself under our standard conditions and measurements. Since a carbon-deuterium bond is stronger than a carbon-hydrogen bond, this lack of a deuterium isotope effect suggests that a carbon-hydrogen bond is not broken in the rate-determining steps of toluenes reactions. 

One might suspect that the relative rates of reactions would favor that of the reaction with toluene. Arguments would mostly likely be based on the fact that the H-CH2Ph bond (87.2kcal/mol) is weaker than that of methane (104.6 kcal/mol). In fact the opposite was observed. The reaction with methane was reported to react 19 times faster than that of the reaction with toluene. The steric bulk of the Ph group inhibits the formation of the intermediate. This was expressed directly in the observation of a larger activation enthalpy of the toluene reaction (A//1 7.1 kcal/... 

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