Acetate reactions carbonylation

The effect of conformation on reactivity is intimately associated with the details of the mechanism of a reaction. The examples of Scheme 3.2 illustrate some of the w s in which substituent orientation can affect reactivity. It has been shown that oxidation of cis-A-t-butylcyclohexanol is faster than oxidation of the trans isomer, but the rates of acetylation are in the opposite order. Let us consider the acetylation first. The rate of the reaction will depend on the fiee energy of activation for the rate-determining step. For acetylation, this step involves nucleophilic attack by the hydroxyl group on the acetic anhydride carbonyl... 

Because all the steps in acetal formation are reversible, the reaction can be driven either forward (from carbonyl compound to acetal) or backward (from acetal to carbonyl compound), depending on the conditions. The forward reaction is favored by conditions that remove water from the medium and thus drive the equilibrium to the right. In practice, this is often done by distilling off water as it forms. The reverse reaction is favored by treating the acetal with a large excess of aqueous acid to drive the equilibrium to the left. 

Under similar reaction conditions, y-acetoxy-jS-methoxyalkenoates are produced when propargylic acetates are carbonylated. The presence of the acetoxy moiety is indispensable it plays the role of an ancillary ligand during the coordination of the triple bond to the palladium(II) species [115]. 

In addition to the activation of carbonyl compounds and imines, Schreiner studied on thiourea-catalyzed acetalization reaction, in which ortho esters were activated by hydrogen bond [19]. Jacobsen has utilized the hydrogen-bond catalysis in reactions with acyliminium ions, wherein hydrogen bond activates the acylim-inium salt through complexation with chloride [20]. 

Figure 6 shows the TPR spectra of adsorbed CO on nickel. The CO was desorbed mostly as the molecular form, whereas the amounts of desorbed carbon dioxide and methane were quite small. Thus, most of the CO adsorbed on nickel is in an undissociated state, and the extent of its adsorption is fairly weak, as the desorption is completed below 200 C. In contrast, the adsorption of methyl acetate on nickel is stronger than those of other reactants or products, as evaluated from the retention time in the nickel-activated carbon column shown in Table III. This fact suggests that most of the nickel is covered by methyl acetate and reaction products, and the coverage of adsorbed CO is quite low under the reaction conditions when the partial pressure of CO is close to that of methyl acetate. The carbonylation is therefore accelerated by increasing the CO/AcOMe ratio which increases the coverage of CO adsorbed competitively with methyl acetate. 

Acetals and ketals are also called glycosides. Acetals and ketals (glycosides) are not in equilibrium with any open chain form. Only hemi-acetals and hemiketal s can exist in equilibrium with an open chain form. Acetals and ketals do not undergo mutarotation or show any of the reactions specific to the aldehyde or ketone groups. For example, they cannot be oxidized easily to form sugar acids. As an acetal, the carbonyl group is effectively protected. 

Acetic Acid. Carbonylation of methanol is the most important reaction in the production of acetic acid.189-192 BASF developed a process applying C0I2 in the liquid phase under extreme reaction conditions (250°C, 650 atm).122 193 The Monsanto low-pressure process, in contrast, uses a more active catalyst combining a rhodium compound, a phosphine, and an iodine compound (in the form of HI, Mel, or T2).122 194—196 Methanol diluted with water to suppress the formation of methyl acetate is reacted under mild conditions (150-200°C, 33-65 atm) to produce acetic acid with 99% selectivity at 100% conversion. 

The catalytic performance of Nafion SAC-13 in the formation of 1,1-diacetates,677 in turn, is very similar to that of HBF4-silica. In the acetalization of carbonyl compounds with ethane-1,2-diol and propane-1,3-diol, products are isolated in good to excellent yields. The formation of THP ethers of alcohols is fast and protected alcohols are isolated in high yields [Eq. (5.238)]. Nafion SAC-13 can also be used in the removal of the THP ether group677 although the transformation requires somewhat longer reaction times (30 min-6 h, 81-97% yield). Furthermore, the catalyst could be recycled in all three processes with practically no loss of activity. 

At the end of his review [7] dealing with the acetalization of carbonyl compounds, Sakurai reported a previously unpublished observation. In the presence of catalytic amounts of iodotrimethylsilane and one equivalent of tetramethoxysilane 38, allyl-trimethylsilane 1 underwent smooth condensation with benzaldehyde 39, leading to adduct 41 in good yield. The silyl-modified Sakurai reaction was born (Scheme 13.15). 

A new, direct route to 0,S-acetals is based in part on the ability of trimethylsilyl triflate to mediate synthesis of 0,0-acetals from carbonyl compounds and silyl ethers (10, 439). Thus reaction of 1 1 mixtures of a silyl ether and phenylthiotrimethylsilane with an aldehyde in the presence of catalytic to stoichiometric amounts of trimethylsilyl triflate can give 0,S-acetals in 37-93% yield. Acetone is amenable to this 0,S-ketalization, but reactions with cyclohexanone result mainly in 0,0-ketals. 

Reactions with Aldehydes and Ketones. Alcohols may combine additively with other carbonyl compounds such addition compounds are known as hemiacetals or acetals (Reaction XVII). 

One can also acetalize carbonyl compounds completely without using the alcohol in excess. This is the case when one prepares dimethyl or diethyl acetals from carbonyl compounds with the help of the ortho formic acid esters trimethyl ortho formate HC(OCH3)3 or triethyl ortho formate HC(OC2H5)3, respectively. In order to understand these reactions, one must first clearly understand the mechanism for the hydrolysis of an orthoester to a normal ester (Figure 9.13). ft corresponds nearly step by step to the mechanism of hydrolysis of 0,0-acetals, which was detailed in Figure 9.12. The fact that the individual steps are analogous becomes very clear (see Figure 9.13) when one takes successive looks at... 

Generally, hypervalent iodine reagents are often better than traditional reagents of similar reactivity, with respect to efficiency and chemoselectivity - sometimes even stereoselectivity. Unusual reactivity is another interesting feature which has often resulted in unexpected transformation. Examples of such reactions may be found in the oxidation of nitrogen-containing compounds, the Hofmann rearrangement in acidic conditions, the acetalization of carbonyl compounds in alkali, the remote functionalization of steroids, etc. Some unique transformations were effected in the... 

Alicyclic, aromatic, aliphatic, steroidal and triterpenoid 1,2-diols are cleaved by iodine triacetate and iodine(I) acetate to generate carbonyl compounds. Aldehydic products are not further oxidized. Iodine triacetate is prepared from iodine trichloride and silver(I) acetate, whereas iodine(I) acetate is prepared from iotUne and silver(I) acetate. Reactions occur in acetic acid at room temperature under nitrogen, and a radical pathway involving a hypoiodite is suggested. The cost and the availability of these reagents are probable reasons for their unpopularity. 

Isoprenylation. In the presence of TiCU or AICI3, this isoprenylsilane (1) reacts with acid chlorides, acetals, and carbonyl compounds to form isoprenylated compounds. Reactions with the first two electrophiles proceed in higher yield than those with carbonyl compounds. Isoprenylation provides simple syntheses of ipsenol (2) and ipsdienol (3), components of the aggregation pheromone of a bark beetle. 

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