Methyl acetate model

Initial theoretical studies focused on steps (1) and (2). Several model systems were examined with ab initio calculations.1191 For the reaction of methyl amine with methyl acetate, it was shown that the addition/elimi-nation (through a neutral tetrahedral intermediate) and the direct displacement (through a transition state similar to that shown in Figure 5a) mechanisms for aminolysis had comparable activation barriers. However, in the case of methyl amine addition to phenyl acetate, it was shown that the direct displacement pathway is favored by approximately 5 kcal/mol.1201 Noncovalent stabilization of the direct displacement transition state was therefore the focus of the subsequent catalyst design process. 

The modeling of RD processes is illustrated with the heterogenously catalyzed synthesis of methyl acetate and MTBE. The complex character of reactive distillation processes requires a detailed mathematical description of the interaction of mass transfer and chemical reaction and the dynamic column behavior. The most detailed model is based on a rigorous dynamic rate-based approach that takes into account diffusional interactions via the Maxwell-Stefan equations and overall reaction kinetics for the determination of the total conversion. All major influences of the column internals and the periphery can be considered by this approach. 

As an application example, the dynamic model was used for the simulation of the steady-state and semibatch production of methyl acetate, performed in a packed column with a catalytic packing. For the model validation, several experiments were carried out in a pilot-plant column. For the investigated operation range, the simulation results are in good agreement with the experimental data. 

Capello et al.16 applied LCA to 26 organic solvents (acetic acid, acetone, acetonitrile, butanol, butyl acetate, cyclohexane, cyclohexanone, diethyl ether, dioxane, dimethylformamide, ethanol, ethyl acetate, ethyl benzene, formaldehyde, formic acid, heptane, hexane, methyl ethyl ketone, methanol, methyl acetate, pentane, n- and isopropanol, tetrahydrofuran, toluene, and xylene). They applied the EHS Excel Tool36 to identify potential hazards resulting from the application of these substances. It was used to assess these compounds with respect to nine effect categories release potential, fire/explosion, reaction/decomposition, acute toxicity, irritation, chronic toxicity, persistency, air hazard, and water hazard. For each effect category, an index between zero and one was calculated, resulting in an overall score between zero and nine for each chemical. Figure 18.12 shows the life cycle model used by Capello et al.16... 

Here we further examine the suitability of QM-SCRF methods in two chemical reactions the base-catalysed hydrolysis of methyl acetate in water, and the steric retardation of Sn2 reactions of chloride with ethyl and neopentyl chlorides in water. In the two cases the influence of the solvent is examined by using the MST version of the PCM model (see ref. [85] for a detailed description). 

To quantitatively understand the preference for the chairlike and boathke transition states of the Claisen rearrangement, Houk et al. carried out a computational study12 (Scheme l.VIII). In the theoretical treatment two methyl acetals, 7Z(OMe) and 7/ (()Me), were used as a model system instead of the fert-butyl-dimethylsilyl (TBS) ketene acetal. Calculations locate four transition states for the rearrangement of 7Z(OMe), among which boathke transition state A is of the lowest energy that leads to the formation of the major isomer observed experimentally. Chairlike transition state B is disfavored, due to steric repulsion between the axial hydrogen of the cyclohexenyl unit and the methoxy substituent of the alkene. 

Figures 4, 5, 6. Comparison between experimental and theoretical conversion histories in emulsion polymerization of methyl methacrylate, styrene, and vinyl acetate. (—), model with gel-effect (—), model without gel-effect.

The earliest theoretical calculations of cocaine hydrolysis focused on the first step of the hydrolysis of the benzoyl ester [57,58]. hi these computational studies [57,58], MNDO, AMI, PM3, and SM3 semiempirical molecular orbital methods, as well as ab initio procedure at the HF/3-21G level of theory, were employed to optimize geometries of the transition states for the first step of the hydrolysis of cocaine and model esters, including methyl acetate [59,60] for which experimental activation energy in aqueous solu-... 

The alkaloid 1 [4] (Scheme 2), for example, has four donor functionalities (a)-(d) that could potentially be involved in the one-electron oxidation. At what site do we expect the oxidation to occur For rapid analysis we approximate the various subunits (a)-(d) by small, structurally related molecules the potentials of which are known. Accordingly, triethylamine and methyl acetate can serve as models for (c) and (d). As donors (a) and (b) are linked by conjugation, we treat them together and, indeed, find with A-acetylindoline a good approximation. 

Low temperature (-50 C) H and F NMR spectra of a- or -substituted ketones, esters and nitriles complexed to boron trifluoride showed that boron coordinates preferentially at the most basic and least-hindered base when more than one coordination site is present in the ligand. Ordinarily a relative measure of chemical shifts for each type of complex would be derived from the spectra of a number of model complexes. For example, F chemical shifts for BF3 complexes of ketones (acetone), esters (methyl acetate), nitriles (acetonitrile) and ethers (diethyl ether) were measured as 149 p.p.m., 150 p.p.m., 144 p.p.m. and 156 p.p.m., respectively. Inspection of the resonance frequency and relative intensities of each peak would then reveal Ae types and ratios of the complexes present in solution. 

Step IV. The "protonated ester" intermediate breaks into choline (or thiocholine) and an acyl enzyme intermediate, modeled here by methyl acetate. 

Arwickar (1981) reported some results for distillation under total reflux conditions of the system acetone-methyl acetate-methanol. The experiments were carried out in a laboratory scale column of 7.62 cm diameter packed with 0.635 cm Raschig rings. The simulation of total reflux operations using the nonequilibrium model is discussed by Krishnamurthy and Taylor (1985a). In simulations of Arwickar s experiments Taylor et al. used the correlations of Onda et al. (1968) to estimate the mass transfer coefficients in each phase and the effective interfacial area. The average absolute discrepancy between predicted and measured mole fractions was less than 2 mol% for acetone and methyl acetate and less than 4 mol% for methanol. 

---