Acetate ions reactions

To see how the data can be used to provide insights into the spin trapping process, PBN would correspond to A with Ea = 1.5 V, and acetate ion to A with E° = 1.5 V (Table 5 gives 1.6 V in acetonitrile, and 1.5 V is therefore somewhat too low, but then it is presumably adequate for dichloromethane). In dichloromethane, the OsvCl6-PBN reaction is estimated to be very fast, more than 6 powers of ten faster than the OsvClg-acetate ion reaction, whereas in acetonitrile the absolute rates are still high but the ratio is only about 50. This difference resides only in the difference between electrostatic factors and illustrates the problems of understanding ET reactions in solvents of even lower dielectric constant such as benzene. 

While this explanation is satisfactory for observations at lower temperatures and in the absence of chloride, the changes in product distribution observed at elevated temperatures and in the presence of chloride reported above are hard to justify. It is possible that at low acetate levels complexes such as XII rather than XIII are the active species and are attacked in a bimolecular reaction by external, nonligand acetate ion (Reaction 12). 

The mechanism of the reaction, which is of the aldol type, involves the car-bonyl group of tlie aldehyde and an active methylene group of the anhydride the function of the basic catalyst B (acetate ion 0H3000 or triethylamine N(0,Hb)j) is to form the anion of the active hydrogen component, i.e., by the extraction of a proton from the anhydride ... 

All these reactions of octadecyl p toluenesulfonate have been reported in the chemical literature and all proceed in synthetically useful yield You should begin by identifying the nucleophile in each of the parts to this problem The nucleophile replaces the p toluenesulfonate leaving group in an Sn2 reaction In part (a) the nucleophile is acetate ion and the product of nucleophilic substitution IS octadecyl acetate... 

When an acid and a base react, the products are a new acid and base. For example, the acetate ion, C1T3COO-, in reaction 6.7 is a base that reacts with the acidic ammonium ion, N1T45", to produce acetic acid and ammonia. We call the acetate ion the conjugate base of acetic acid, and the ammonium ion is the conjugate acid of ammonia. 

Weak bases only partially accept protons from the solvent and are characterized by a base dissociation constant, kj,. For example, the base dissociation reaction and base dissociation constant for the acetate ion are... 

Solid Compounds. The tripositive actinide ions resemble tripositive lanthanide ions in their precipitation reactions (13,14,17,20,22). Tetrapositive actinide ions are similar in this respect to Ce . Thus the duorides and oxalates are insoluble in acid solution, and the nitrates, sulfates, perchlorates, and sulfides are all soluble. The tetrapositive actinide ions form insoluble iodates and various substituted arsenates even in rather strongly acid solution. The MO2 actinide ions can be precipitated as the potassium salt from strong carbonate solutions. In solutions containing a high concentration of sodium and acetate ions, the actinide ions form the insoluble crystalline salt NaM02(02CCH2)3. The hydroxides of all four ionic types are insoluble ... 

The initiating step in these reactions is the attachment of a group to the sulfoxide oxygen to produce an activated intermediate (5). Suitable groups are proton, acyl, alkyl, or almost any of the groups that also initiate the oxidations of alcohols with DMSO (40,48). In a reaction, eg, the one between DMSO and acetic anhydride, the second step is removal of a proton from an a-carbon to give an yUde (6). Release of an acetate ion generates the sulfur-stabilized carbonium ion (7), and the addition of acetate ion to the carbonium ion (7) results in the product (eq. 15) ... 

Entry 4 shows that reaction of a secondary 2-octyl system with the moderately good nucleophile acetate ion occurs wifii complete inversion. The results cited in entry 5 serve to illustrate the importance of solvation of ion-pair intermediates in reactions of secondary substrates. The data show fiiat partial racemization occurs in aqueous dioxane but that an added nucleophile (azide ion) results in complete inversion, both in the product resulting from reaction with azide ion and in the alcohol resulting from reaction with water. The alcohol of retained configuration is attributed to an intermediate oxonium ion resulting from reaction of the ion pair with the dioxane solvent. This would react until water to give product of retained configuratioiL When azide ion is present, dioxane does not efiTectively conqiete for tiie ion-p intermediate, and all of the alcohol arises from tiie inversion mechanism. ... 

An apparently related reaction involves iodination in pure methanol in the presence of calcium chloride. The main product is the 21,21-d3-iodo derivative, which on reaction with acetate ion gives, surprisingly, the 21-monoacetate ... 

While displacement of a 21-bromide by hydroxyl can be accomplished by careful control of reaction conditions,it is preferable to use acetate ion instead, and potassium acetate in refluxing acetone has been most commonly... 

What product would you expect to obtain from a nucleophilic substitution reaction of (S)-2-bromohexane with acetate ion, CH3CO2- Assume that inversion of configuration occurs, and show the stereochemistry of both reactant and product. 

Nucleophilicity roughly parallels basicity when comparing nucleophiles that have the same reacting atom. For example, OH- is both more basic and more nucleophilic than acetate ion, CH3CO2-, which in turn is more basic and more nucleophilic than H20. Since "nucleophilicity" is usually taken as the affinity of a Lewis base for a carbon atom in the Sfj2 reaction and "basicity" is the affinity of a base for a proton, it s easy to see why there might be a correlation between the two kinds of behavior. 

Notice in both of the previous reactions that only "half" of the anhydride molecule is used the other half acts as the leaving group during the nucleophilic acyl substitution step and produces acetate ion as a by-product. Thus, anhydrides are inefficient to use, and acid chlorides are normally preferred for introducing acyl substituents other than acetyl groups. 

This is a typical nucleophilic acyl substitution reaction, with p-hvdroxyaniline as the nucleophile and acetate ion as the leaving group. 

Make a table like the one above and determine the number of moles of acetic acid (HAc) and acetate ion (Ac-) after the reaction is complete. Since the stoichiometric ratios are 1 1, the limiting reactant is the one with the smaller number of moles. 

Notice that this reaction is the reverse of the reaction of the weak base QH - (the acetate ion) with water (Chapter 13). It follows from the reciprocal rule that for this reaction,... 

When the conjugate acid of aniline, C6H5NH3+, reacts with the acetate ion, the following reaction takes place ... 

Urea possesses negligible basic properties (Kb = 1.5 x 10 l4), is soluble in water and its hydrolysis rate can be easily controlled. It hydrolyses rapidly at 90-100 °C, and hydrolysis can be quickly terminated at a desired pH by cooling the reaction mixture to room temperature. The use of a hydrolytic reagent alone does not result in the formation of a compact precipitate the physical character of the precipitate will be very much affected by the presence of certain anions. Thus in the precipitation of aluminium by the urea process, a dense precipitate is obtained in the presence of succinate, sulphate, formate, oxalate, and benzoate ions, but not in the presence of chloride, chlorate, perchlorate, nitrate, sulphate, chromate, and acetate ions. The preferred anion for the precipitation of aluminium is succinate. It would appear that the main function of the suitable anion is the formation of a basic salt which seems responsible for the production of a compact precipitate. The pH of the initial solution must be appropriately adjusted. 

The addition of acetate ion to an arenediazonium ion is also an O-coupling. As the equilibrium of this reaction lies very much to the side of the starting ions (Suschitzky, 1967), and since diazoacetates play an important role as transient intermediates in homolytic reactions of A-nitrosoacetanilides, we will discuss diazoacetates in that context (Sec. 10.10). 

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