Benzoates tests

For the detection of solvent-extracted oils (in which carbon disulphide is used) the Olive Oil Committee of the American Oil Chemists Society recommends the silver benzoate test. 

Sodium benzoate,—Burns with great difficulty, and after prolonged heating leaves a white infusible residue of NajCOj. Scrape this residue into a test-tube, and test for carbonate in the usual way. Typical of alkali salts of carboxylic acids. 

Add 1 ml. of the alcohol-free ether to 0-1-0-15 g. of finely-powdered anhydrous zinc chloride and 0 5 g. of pure 3 5-dinitrobenzoyl chloride (Section 111,27,1) contained in a test-tube attach a small water condenser and reflux gently for 1 hour. Treat the reaction product with 10 ml. of 1-5N sodium carbonate solution, heat and stir the mixture for 1 minute upon a boiling water bath, allow to cool, and filter at the pump. Wash the precipitate with 5 ml. of 1 5N sodium carbonate solution and twice with 6 ml. of ether. Dry on a porous tile or upon a pad of filter paper. Transfer the crude ester to a test-tube and boil it with 10 ml. of chloroform or carbon tetrachloride filter the hot solution, if necessary. If the ester does not separate on cooling, evaporate to dryness on a water bath, and recrystallise the residue from 2-3 ml. of either of the above solvents. Determine the melting point of the resulting 3 5 dinitro benzoate (Section 111,27). 

Benzoates. Dissolve 0-5 g. of the amino acid in 10 ml. of 10 per cent, sodium bicarbonate solution and add 1 g. of benzoyl chloride. Shake the mixture vigorously in a stoppered test-tube remove the stopper from time to time since carbon dioxide is evolved. When the odour of benzoyl chloride has disappeared, acidify with dilute hydrochloric acid to Congo red and filter. Extract the solid with a little cold ether to remove any benzoic acid which may be present. RecrystaUise the benzoyl derivative which remains from hot water or from dilute alcohol. 

Self-Test 11.4B Calculate the ratio of the molarities of benzoate ions and benzoic acid (C6H,COOH) needed to buffer a solution at pH = 3.50. The pKa of C6H,COOH is 4.19. 

The intermediates 74 and 76 can now lose OR to give the acid (not shown in the equations given), or they can lose OH to regenerate the carboxylic ester. If 74 goes back to ester, the ester will still be labeled, but if 76 reverts to ester, the 0 will be lost. A test of the two possible mechanisms is to stop the reaction before completion and to analyze the recovered ester for 0. This is just what was done by Bender, who found that in alkaline hydrolysis of methyl, ethyl, and isopropyl benzoates, the esters had lost 0. A similar experiment carried out for acid-Catalyzed hydrolysis of ethyl benzoate showed that here too the ester lost However, alkaline hydrolysis of substimted benzyl benzoates showed no loss. This result does not necessarily mean that no tetrahedral intermediate is involved in this case. If 74 and 76 do not revert to ester, but go entirely to acid, no loss will be found even with a tetrahedral intermediate. In the case of benzyl benzoates this may very well be happening, because formation of the acid relieves steric strain. Another possibility is that 74 loses OR before it can become protonated to 75. Even the experiments that do show loss do not prove the existence of the tetrahedral intermediate, since it is possible that is lost by some independent process not leading to ester hydrolysis. To deal with this possibility. Bender and Heck measured the rate of loss in the hydrolysis of ethyl trifluorothioloacetate- 0 ... 

The synthesis of this derivative of KDG was accomplished following the sequence depicted in figure 6. Methylation of the intermediate 8 with methyl Inflate afforded compotmd 21. Subsequent removal of the enol benzoate group at C-2 and of the silyl ether at C-6 provided the target compound 23 in 11% overall yield based on 8. This low yield could be due to the unstability of compotmds 8, 21 and 22 in a basic medium. However 24 was obtained in quantity sufficient for testing. 

Now a very useful feature of the excess acidity method comes into play likely nucleophiles or bases can be tested by subtracting their log activities or concentrations from the left-hand side of equations (59) and (60), and the species reacting with SH+ is uniquely identified when linearity of the result against X is achieved.145,161 For instance, subtraction of twice the water activity is required to attain linearity in ester hydrolysis processes such as equation (42), as shown in Fig. 11 for methyl benzoate41 and ethyl benzoate.210 The water activities given in Table 3 were used. The parameters of the lines in Fig. 11, obtained by curve-fitting, are methyl benzoate, slope 0.921 + 0.010, intercept... 

In the case of the benzyloxytrityl-hydroxylamineresin 24b, the starting material is the Merrifield resin, chloromethylated polystyrene (1.7 mmol Cl x g 1) which is treated with 3 equiv. of 4-hydroxy-methyl benzoate in DMA with sodium methylate as base. The Beilstein test is used for monitoring and microanalyses showed the absence of chloride (Scheme 6). 

A number of researchers have also used a proposed ASTM test mixture, benzaldehyde, acetophenone, methyl benzoate, dimethyl terphtha-late, benzyl alcohol, and benzene to demonstrate separation on a column [98]. However the first four compounds are from the same interaction group and should behave in the same way on changing conditions. The first three have almost constant indices (respectively 760, 800, and 890) so that in effect they create an index scale with constant differences against which the last two compounds can be compared [96,99]. 

FIGURE 8 Analysis of the test mixture with (A) the SDS MEKC system containing 10 mM phosphate buffer (pH 7.5), 60 mM SDS, and 10% acetonitrile and (B) the CTAB MEKC system containing 25 mM phosphate buffer (pH 7.5), 10 mM CTAB, and 10% acetonitrile. Peaks I formamide 2 pyridine 3 aniline 4 meta-cresol 5 phenyl acetate 6 nitrobenzene 7 benzoic acid 8 thiamine 9 ethyl benzoate. (Reprinted from reference 270, with permission.)... 

Systematic investigations were carried out for the preparation of cellulose acetate of D.S. 2,65 and other mixed esters which included cellulose acetate-propionate, cellulose acetate-butyrate, cellulose acetate-benzoate and cellulose acetate-methacrylate. The experimental conditions were optimised for maximum yield of the ester. Flat osmotic membranes were developed from these esters and characterised for their osmotic and transport properties. The nmmbra-nes were evaluated in a reverse osmosis laboratory test-cell using 5OOO ppm sodium chloride solution at 40 bars pressure. Table 1 presents the typical performance data of these membranes. 

---