Franchimont reaction

Franchimont reaction. Carboxylic acid dimerization to 1,2-dicarboxylic acids by treating a-bromocarboxylic acids with potassium cyanide followed by hydrolysis and decarboxylation. 

Forster Diazoketone Synthesis Forster Reaction Four-Component Condensation Franchimont Reaction Frankland Synthesis Frankland-Duppa Reaction Freund Reaction... 

In the Franchimont test [42], nitramines are reduced to nitrite ions by zinc and acetic acid and then subjected to the Griess reaction. A modification of this test was used for the identification of nitramine impurities in RDX [43]. 

The concentration of alkali required depends on the properties of the radicals R and R1. The more electrophilic the radicals and the more dcidic the nitramine, the easier the course of reaction. Secondary nitramines are decomposed by an aqueous solution of sodium hydroxide. The reaction conditions, including the concentrations of NaOH solutions differ according to the substance. Van Erp and Franchimont [21] found that the reaction proceeded by the following mechanism ... 

This type of reaction can be illustrated by the nitration of methylamine according to Franchimont [37] (6) ... 

CH2-N(N02).CH2.CH2.N(N02).C2H5 mw 382.34, N 29.51% crysts (from ale), mp 96.5-96.8° sol in ale insol in alkalies gives a positive Franchimont test for nitra-mine was prepd from a suspension of tri-ethylenetetranitramine in eth soln contg diazoethane, which reaction evolved gas rapidly, and on evaporation of the ether left a sirup which gradually solidified during four days (Ref 2). This is an expl compd Refs 1) Beil - not found 2) G.N.R. Smart G.F. Wright, JACS 70, 3142(1948) Ca 43, 570(1949)... 

Chatenoud L, Ferran C, Reuter A, Legendre C, Gevaert Y, Kreis H, Franchimont P, Bach JF Systemic reaction to the anti-T-cell monoclonal anti body OKT3 in relation to serum levels of tumor necrosis factor and interferon-gamma [corrected], N Engl J Med 1989,320 1420-1421... 

Franchimont (1890) observed that nitrosomethyl carbamates evolved a yellow gas when treated with alkali, and von Pechmann (1894, 1895), after investigating the reaction carefully, established the structure CH2N2 for diazomethane. He recognized its close relationship to diazoacetates and the differences between it and aromatic diazo compounds. The preparation follows Scheme 2-16. 

This reaction was initially reported by Franchimont in 1872. It is a condensation of two a-bromocarboxylic acids in absolute alcohol in the presence of sodium cyanide to give 1,2-dicarboxylic acids after hydrolysis and decarboxylation. In the case of a-bromoketones, 1,4-diketones are produced similarly after hydrolysis with phosphoric acid. It was found that the bulky group at the ester end prevents condensation, as in the case of phenyl and naphthyl esters. Although the substituent at j0-position does not prevent such condensation, it reduces the overall yield. In addition, a compound with two ester groups at proper position will form cyclic diacid under such reaction conditions and cyclobutane, " cyclopentane and cyclohexane dicarboxylic acid have been prepared in such a way. In the case of l,4-dibromo-l,4-dibenzoylbutane, a derivative of cyclopentanone is produced after acidic hydrolysis. It should be pointed out that other common solvents—including acetone, ether, and acetonitrile- are not good for this reaction. ... 

---