Benzoate ester Subject

In fact p for the acid-catalyzed hydrolysis and formation of benzoate esters is small, and since the fit to the Hammett equation is characteristically rather poor for these reactions, p is often taken as zero. Some typical values are listed in Table 16. Too much weight should not be attached to the absolute values of the reaction constants given in the table. The data do not fit the Hammett equation accurately, and it is known that much of the earlier work was subject to considerable error, because no allowance was made for the slow reaction of the catalyst with the solvent. This could affect the observed rate coefficients in three ways—by reducing the catalyst concentration, by decreasing the acid content as measured by titration, and by producing water, e.g. 

As before, the hydroxy group of this epoxy alcohol was subjected to a Mitsonobu esterification and subsequent cleavage of the resulting benzoate ester 14 to afford epoxy alcohol 15, with the desired relative stereochemistry, in 87 % yield over two steps. The free hydroxy group was protected, as previously, with a benzyl group in 96 % yield. 

In an extension of the work described m the preceding section Bender showed that basic ester hydrolysis was not concerted and like acid hydrolysis took place by way of a tetrahedral intermediate The nature of the experiment was the same and the results were similar to those observed m the acid catalyzed reaction Ethyl benzoate enriched m 0 at the carbonyl oxygen was subjected to hydrolysis m base and samples were isolated before saponification was complete The recovered ethyl benzoate was found to have lost a por tion of Its isotopic label consistent with the formation of a tetrahedral intermediate... 

It should be mentioned that the Food Additives Analytical Manual (FAAM) [75] provides analysts with FDA evaluated methodology (partly subjected to collaborative study) needed to determine compliance with food additive regulations, including procedures for indirect food additives, such as butylated hydroxy-anisole (BHA), butylated hydroxytoluene (BHT), t-butylhydroxyquinone (TBHQ), dilaurylthiopropionate (DLTDP), fatty acid methyl esters (FAME), sodium benzoate, sorbitol, and others. 

The cooled reaction product is treated with 200 cc. of water, the layer of oil separated, washed once with a second portion of water, and subjected to distillation in vacuo. The first fraction of the distillate contains benzyl alcohol together with unchanged aldehyde, as well as a small quantity of water. The temperature then rises rapidly to the boiling-point of benzyl benzoate, when the receivers are changed. The product boils at 184-185°/15 mm., and analysis by saponification shows it to consist of 99 per cent ester. A yield of 410-420 g. is obtained, which corresponds to 90-93 per cent of the theoretical amount. This benzyl benzoate supercools readily, but after solidifying... 

Extension of the C-tether to m = 2 can be achieved by subjecting diazo ketone 58 to the Wolff rearrangement using silver benzoate, triethyl-amine and methanol. Hydrolysis of the resulting methyl 4-methyl-4-[(E)-phenyldiazenyllpentanoate (74) (94%) yields the acid 75 (84%). Conversion of 75 into the mixed anhydride 76 followed by treatment with diazomethane gives 1 -diazo-5-methyl-5-[(E)-phenyldiazenyl]hexan-2-one (77) in low yield (19%) and methyl ester 74 (78%) (Scheme 18). 

The preparations of dextran, and certain ethers and esters of dextran have been the subjects of about fifteen recent patents. The dextran (of L. mesenteroides or dextraniczim) may be precipitated first from the culture by the addition of ethanol or acetone, or the culture itself may be treated directly with the appropriate halide and sodium hydroxide in either a single stage or a two-stage procedure. The benzyl ether of dextran, formed by the reaction of dextran with benzyl chloride and sodium hydroxide at 75-185° for three to ten hours, is soluble in acetone and other solvents, and may be used in lacquers. Mixed ether and ester derivatives of dextran, e. g., benzyl and phthalate or butyl and benzoate, have been used for forming films, coatings or molded products. A preparation of dextran acetate has also been patented. ... 

The most important species in the mechanism for ester hydrolysis is the tetrahedral intermediate. Evidence in support of the existence of the tetrahedral intermediate was developed by Professor Myron Bender on the basis of isotopic labeling experiments he carried out at the University of Chicago. Bender prepared ethyl benzoate, labeled with the mass-18 isotope of oxygen at the carbonyl oxygen, then subjected it to acid-catalyzed hydrolysis in ordinary (unlabeled) water. He found that ethyl benzoate, recovered from the reaction before hydrolysis was complete, had lost a portion of its isotopic label. This observation is consistent only with the reversible formation of a tetrahedral intermediate under the reaction conditions ... 

Chlorosulfonyl benzoates were synthesized from 2-aryldimethyloxazolines 17 (Scheme 5). Sequential treatment with n-butyllithium and dipropyl disulfide afforded sulfides 18. The oxazolines 18 were then hydrolyzed to the benzoic acids 19 under acidic conditions. Fisher esterification gave the esters 20, which were oxidized to the corresponding sulfonyl chlorides 21 using chlorine and aqueous acetic acid. When methoxy-substituted benzoic acids (19, X = OMe) were employed, further manipulations were performed prior to oxidation. For example, phenol (22) was prepared by demethylation with boron tribromide, subjected to esterification, and then alkylated by a variety of electrophiles to provide 23. As before, 23 was oxidized using chlorine and aqueous acetic acid. 

Ethers are oxidized to esters by benzyltriethylammonium permanganate for example benzyl n-butyl ether gives butyl benzoate (90%) and methyl n-octyl ether is converted into methyl octanoate (41%). However, it must be added that this reagent explodes violently when heated or subjected to shock it should not be stored for any length of time. Alcohols (RCH2OH) can be directly oxidized to esters (RCO2CH2R) electrolytically in ca. 80% yield when iodonium ions are used as catalytic electron carriers. ... 

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