Proposed mechanisms

Typically, boronic acids are used in an excess, and a more efficient protocol has been developed which not only proceeds in the absence of a base, but also uses equimolar amounts of imidazole and boronic acid. These processes are best 

The use of potassium aryltrifluoroborate salts as useful bench-stable alternatives to arylboronic acids has been demonstrated in O—H bond arylations (vide supra), 

Me / S=NH Q° Base-free, generally high yields (62-93%), wide substrate scope in aryl boronic add Cu(OAc)2 (O.lequiv), ArB(OH)2 (2.3equiv), MeOH (0.3M),rt, 12h 

Interestingly, in contrast to the numerous intramolecular couplings between alcohols and aryl boronic acids [lb], there are no reports of intramolecular copper-catalyzed N—H bond arylahons with boronic acids. 

Several lines of evidence point to substrate (H and H2) binding to a terminal (vs. bridging) site on the Fe center distal from the Fe4 cluster (1) CO inhibition involves binding at this site, (2) in the and states, this site is either vacant or occupied by exchangeable ligands, (3) the central atom of the dithiolate cofactor, which is thought to have a functional role, is tilted toward this site, and (4) the hydrophobic, H2-conveying tunnel terminates at this Fe site. 

A catalytic cycle begins with le reduction of in which the proximal iron becomes Fe(l) (Fq. 12.3). Reduction shifts the bridging CO ligand to a terminal position on the distal Fe. 

The dinuclear active site of the Fe-H2ase is reminiscent of Fe2(SR)2(CO)g species, which were discovered in the 1920s [27,28] and well developed in the 1960-1980s [29-31]. Attesting to their considerable stability, these hexacarbonyls arise via many pathways, but commonly synthesis entails the reactions of iron carbonyls with the corresponding thiol or disulfide. 

Addition of two equivalents of CN to Fe2(SR)2(CO)g efficiently yields [Fe2(SR)2(CN)2(CO)4] for a wide range of substituents R, including both chelating and simple thiolates (Fig. 12.2) [32-34]. The dicyanide forms particularly 

---

Process 2, the adsorption of the reactant(s), is often quite rapid for nonporous adsorbents, but not necessarily so it appears to be the rate-limiting step for the water-gas reaction, CO + HjO = CO2 + H2, on Cu(lll) [200]. On the other hand, process 4, the desorption of products, must always be activated at least by Q, the heat of adsorption, and is much more apt to be slow. In fact, because of this expectation, certain seemingly paradoxical situations have arisen. For example, the catalyzed exchange between hydrogen and deuterium on metal surfaces may be quite rapid at temperatures well below room temperature and under circumstances such that the rate of desorption of the product HD appeared to be so slow that the observed reaction should not have been able to occur To be more specific, the originally proposed mechanism, due to Bonhoeffer and Farkas [201], was that of Eq. XVIII-32. That is. 

Treatment of 192 with dimethyl acetylenedicarboxylate yields a thiophene derivative (195) when R = Ph and a 2-p3Tidone (1S>6) derivative when R = H (Scheme 100). The proposed mechanism involves the formation of a mesoionic derivative (193) initially further dipolar addition yields adduct 194, the decomposition of which is dependent on the R substituent as described for related compounds (435). ... 

The generally accepted mechanism for this reaction is presented as a series of three equa tions m Figure 4 6 We say generally accepted because a reaction mechanism can never be proved to be correct A mechanism is our best present assessment of how a reaction proceeds and must account for all experimental observations If new experimental data appear that conflict with the mechanism the mechanism must be modified to accom modate them If the new data are consistent with the proposed mechanism our confl dence grows that the mechanism is likely to be correct... 

Each equation m Figure 4 6 represents a single elementary step An elementary step IS one that involves only one transition state A particular reaction might proceed by way of a single elementary step m which case it is described as a concerted reaction, or by a series of elementary steps as m Figure 4 6 To be valid a proposed mechanism must meet a number of criteria one of which is that the sum of the equations for the elementary steps must correspond to the equation for the overall reaction Before we examine each step m detail you should verify that the mechanism m Figure 4 6 satisfies this requirement... 

According to the proposed mechanism for biological 0x1 dation of ethanol the hydrogen that is transferred to the coenzyme comes from C 1 of ethanol Therefore the dihydropyridme ring will bear no deuterium atoms when CD3CH2OH IS oxidized because all the deuterium atoms of the alcohol are attached to C 2... 

FIGURE 27 19 Proposed mechanism of hydrolysis of a peptide catalyzed by carboxypeptidase A The peptide is bound at the active site by an ionic bond between its C terminal ammo acid and the positively charged side chain of arginine 145 Coordination of Zn to oxygen makes the carbon of the carbonyl group more positive and increases the rate of nucleophilic attack by water... 

Lower alkanes such as methane and ethane have been polycondensed ia superacid solutions at 50°C, yielding higher Hquid alkanes (73). The proposed mechanism for the oligocondensation of methane requires the involvement of protonated alkanes (pentacoordinated carbonium ions) and oxidative removal of hydrogen by the superacid system. 

The proposed mechanism for producing ethanol [64-17-5] from butane involves -scission of a j -butoxy radical (eq. 38). The j -butoxy radicals are derived from j -butylperoxy radicals (reaction 14 (213)) and/or through some sequence involving reaction 33. If 25% of the carbon forms ethanol, over 50% must pass through the j -butoxy radical. Furthermore, the principal fate of j -butoxy radicals must be the P-scission reaction the ethoxy radical, on the other hand, must be converted to ethanol efficiently. 

The proposed mechanism by which chlorinated dioxins and furans form has shifted from one of incomplete destmction of the waste to one of low temperature, downstream formation on fly ash particles (33). Two mechanisms are proposed, a de novo synthesis, in which PCDD and PCDF are formed from organic carbon sources and Cl in the presence of metal catalysts, and a more direct synthesis from chlorinated organic precursors, again involving heterogeneous catalysis. Bench-scale tests suggest that the optimum temperature for PCDD and PCDF formation in the presence of fly ash is roughly 300°C. 

A proposed mechanism for toughening of mbber-modifted epoxies based on the microstmcture and fracture characteristics (310—312) involves mbber cavitation and matrix shear-yielding. A quantitative expression describes the fracture toughness values over a wide range of temperatures and rates. 

Although the alkylation of paraffins can be carried out thermally (3), catalytic alkylation is the basis of all processes in commercial use. Early studies of catalytic alkylation led to the formulation of a proposed mechanism based on a chain of ionic reactions (4—6). The reaction steps include the formation of a light tertiary cation, the addition of the cation to an olefin to form a heavier cation, and the production of a heavier paraffin (alkylate) by a hydride transfer from a light isoparaffin. This last step generates another light tertiary cation to continue the chain. 

DCHA is normally obtained in low yields as a coproduct of aniline hydrogenation. The proposed mechanism of secondary amine formation in either reductive amination of cyclohexanone or arene hydrogenation iHurninates specific steps (Fig. 1) on which catalyst, solvents, and additives moderating catalyst supports all have effects. 

Pig. 2. Proposed mechanism of inbition of smooth muscle contraction by P2" gonists, where AMP is adenosine monophosphate, cAMP is cycHc-3 5 adenosine monophosphate, ATP is adenosine triphosphate, and -P is an attached phosphate. 

The first mechanistic studies of silanol polycondensation on the monomer level were performed in the 1950s (73—75). The condensation of dimethyl sil oxanediol in dioxane exhibits second-order kinetics with respect to diol and first-order kinetics with respect to acid. The proposed mechanism involves the protonation of the silanol group and subsequent nucleophilic substitution at the siHcone (eqs. 10 and 11). 

Inhibitors are often iacluded ia formulations to iacrease the pot life and cute temperature so that coatings or mol dings can be convenientiy prepared. An ideal sUicone addition cure may combine iastant cure at elevated temperature with infinite pot life at ambient conditions. Unfortunately, real systems always deviate from this ideal situation. A proposed mechanism for inhibitor (I) function is an equUibtium involving the inhibitor, catalyst ligands (L), the sUicone—hydride groups, and the sUicone vinyl groups (177). 

Table 4 contains products available for Factor VII, Factor VIIFC (hemophilia A), Factor IX, and von Willebrand protein deficiency. Table 5 fists miscellaneous hemostatics and thein proposed mechanisms of action. 

P-Adrenoceptor Blockers. There is no satisfactory mechanism to explain the antihypertensive activity of P-adrenoceptor blockers (see Table 1) in humans particularly after chronic treatment (228,231—233). Reductions in heart rate correlate well with decreases in blood pressure and this may be an important mechanism. Other proposed mechanisms include reduction in PRA, reduction in cardiac output, and a central action. However, pindolol produces an antihypertensive effect without lowering PRA. In long-term treatment, the cardiac output is restored despite the decrease in arterial blood pressure and total peripheral resistance. Atenolol (Table 1), which does not penetrate into the brain is an efficacious antihypertensive agent. In short-term treatment, the blood flow to most organs (except the brain) is reduced and the total peripheral resistance may increase. 

Pulping. Mechanical and/or chemical methods are used for pulping. Lignin softens at lower temperatures than ceUulose, a difference that is the main basis for the separation. The exact stmcture of lignin is unknown and proposed mechanisms of deUgnification are somewhat speculative. Removal of... 

Equation 22 gives the maximum theoretical obtainable chlorine dioxide from the disproportionation of HCIO,. Experimentally, differences in the stoichiometry have been reported. This is because the chloride formed in equation 21 can catalyze the reaction to form more chlorine dioxide as in equation 22. Proposed mechanisms for these reactions and the kinetics under various conditions have been described (16,108). 

Fig. 5. Proposed mechanism of iaactivation of a-chymotrypsia by the pseudoirreversible inhibitor 2-ethoxy-4Ff-3,l-benz-oxazia-4-one. A substituted...

IV-Methylated pyridazinones can be obtained from 3,6-dialkoxypyridazines by treatment with alkyl halides or dialkyl sulfates. Methyl iodide and dimethyl sulfate are most frequently used. According to the proposed mechanism, an intermediate quaternary pyridazinium salt is formed, followed by elimination of a group R from the alkoxy group. At higher temperature, l,2-dimethylpyridazine-3,6(l//,2//)-dione is formed with dimethyl sulfate. 

The important synthesis of pyrazoles and pyrazolines from aldazines and ketazines belongs to this subsection. Formic acid has often been used to carry out the cyclization (66AHQ6)347) and N-formyl-A -pyrazolines are obtained. The proposed mechanism (70BSF4119) involves the electrocyclic ring closure of the intermediate (587) to the pyrazoline (588 R = H) which subsequently partially isomerizes to the more stable trans isomer (589 R = H) (Section 4.04.2.2.2(vi)). Both isomers are formylated in the final step (R = CHO). 

The quantitative computations were conducted using equilibrium thenuodynamic model. The proposed model for thermochemical processes divides layer of the sample into contacting and non-contacting zones with the material of the atomizer. The correlation of all initial components in thermodynamic system has been validated. Principles of results comparison with numerous experimental data to confirm the correctness of proposed mechanism have been validated as well. 

At this point in the investigation, the relationship between the pits and the arrowhead-shaped regions of corrosion was uncertain. Several possible causes for the pitting were considered, such as siphonic gas exsolution, biological and/or microbiological activity, and debris (concrete chips, etc.) lodged in the tubes, but each was tentatively dismissed as improbable since none of the proposed mechanisms adequately accounted for all observations. 

Figure 5 Proposed mechanism for biosynthetie introduetion of bromine and ehlorine atoms into the Lcmrencia sesquiterpenoid nidifieine (24)...

---