Silver 3,5-dinitrobenzoate

To a mixture of 75 mL dry chloroform and 9.5 g silver 3,5-dinitrobenzoate (0.03 mol) cooled in an ice-salt mixture a solution of 0.03 mol iodine dissolved in 20 mL dry chloroform was added over 10-15 min with shaking. 1-Butene was then passed into the solution for 15 min with continuous shaking. The solid silver iodide that precipitated was removed, and the filtrate was washed with six 25-mL portions of 5% sodium carbonate solution. The chloroform solution was then dried over Drierite, the chloroform was removed by distillation, and boiling petroleum ether was added to dissolve the ester. The solution was then cooled, and l-iodo-2-butanol 3,5-dinitrobenzoates was removed and purified by recrystallization from petroleum ether, in a yield of 46%. 

Procedure A suspension of 50 mg of silver 3,5-dinitrobenzoate, 2 ml of benzene, and a drop of alkyl iodide in a sealed glass ampoule is heated at 100 °C for 120 min. After cooling and opening of the ampoule the benzene solution is applied onto the chromatogram either directly or, if necessary, after concentration. 

Fig. 31. Ampoule for the absorption of alkyl iodides, cooled with ice and filled with a suspension of silver 3,5-dinitrobenzoate in benzene.

Ethy1-2,6-dinitrobenzoate, crysts (from ale), rap 74.7°. It may be prepd from the silver salt of the acid and ethyl iodide Ref Beil. 9, 413... 

Ethyl-3,5-dinitrobenzoate, ndls (from ale), sp gr 1.295 at 111°, mp 91—2°, bp — not given insol in w si sol in ale. It may be prepd from the silver salt of the acid and ethyl iodide, from the acid and ale HC1 . from the acid chloride in benzene from the chloride and ether with zinc chloride... 

When a non-polar solvent was used in silver ion-catalysed reactions of this type, the 3a-iodo-2j0-trifiuoroacetate [xog] and 3a"iodO"2/ -(3,5-dinitrobenzoate) [xxo] were obtained from the corresponding silver salts. It seems likely that the electron-withdrawing character of these ester groups prevents their participation in displacement of the iodine from the 3a-position, for the benzoate and chlorobenzoate reacted normally [xix] leading to the corresponding ZfXMs-diesters [xxo ]. 

Benzoyl hypoiodite, C HsCOOI, a similar complex with similar applications, is formed from iodine and 2 mol of silver benzoate [783, 784], Silver p-chloro- and 3,5-dinitrobenzoates react analogously [783] (equation 17). 

Another possibility to chromatograph alkyl halides on paper consists in their conversion to alkyl 3,5-dinitrobenzoates with the silver salt of 3,5-dinitrobenzoic acid according to the equation... 

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