2.4- Dinitrofluorobenzene, alkylation

The Fischer synthesis gives a 2,3,3-trialkylindolenine (8) which is subsequently alkylated on the N atom to give the 1,2,3,3-tetraalkylindoleninium salt (9) (Scheme 6). Arylation, however, for example, with 2,4-dinitrofluorobenzene or 4-nitrohalo-benzenes, has not been successful. 7... 

Aliphatic and aromatic nucleophilic substitution reactions are also subject to micellar effects, with results consistent with those in other reactions. In the reaction of alkyl halides with CN and S Oj in aqueous media, sodium dodecyl sulfate micelles decreased the second-order rate constants and dodecyltrimethylammonium bromide increased them (Winters, 1965 Bunton, 1968). The reactivity of methyl bromide in the cationic micellar phase was 30 to 50 times that in the bulk phase and was negligible in the anionic micellar phase a nonionic surfactant did not significantly affect the rate constant for n-pentyl bromide with S2O3-. Micellar effects on nucleophilic aromatic substitution reactions follow similar patterns. The reaction of 2, 4-dinitrochlorobenzene or 2, 4-dinitrofluorobenzene with hydroxide ion in aqueous media is catalyzed by cationic surfactants and retarded by sodium dodecyl sulfate (Bunton, 1968, 1969). Cetyltrimethylammonium bromide micelles increased the reactivity of dinitrofluorobenzene 59 times, whereas sodium dodecyl sulfate decreased it by a factor of 2.5 for dinitrochlorobenzene, the figures are 82 and 13 times, respectively. A POE nonionic surfactant had no effect. 

Treatment of the isoquinoline Reissert compound (2) with sodium hydride in dimethylformamide,96 with 50% aqueous sodium hydroxide-TEBA chloride,61 or with 50% aqueous sodium hydroxide-TBA chloride963 and an activated aryl halide, such as 2,4-dinitrofluorobenzene,96 2-bromo-3-nitropyridine,96 4-nitrochlorobenzene,61 t-butyl 2-chloro-5-nitrobenzoate,61 2-chloro-3-nitropyridine,963 4-chloro-3-nitropyridine,96a or 9-chloroacri-dine96b leads to the arylation product 43. Arylation of the quinoline Reissert compound (1) with 4-nitrofluorobenzene in the presence of sodium hydride in dimethylformamide leads to 44.96 It should be noted that alkylation of... 

The synthesis of methyl D-mannoside 6-phosphate, shown in Scheme 6, has been executed on a 35 g scale. The method has also been applied, on a smaller scale, to the preparation of several other alkyl hexoside 6-phosphates and, with minor changes, to that of D-mannose 6-phosphate. Several monosaccharide phosphates have been converted to their phosphofluoridates by use of 2,4-dinitrofluorobenzene, and the mechanism of the reaction has been discussed. ... 

An alkylator which has found use in analytical work (sequencing of proteins the determination of the sequence in which the amino acid monomers are arranged in the protein polymer) is 2,4-dinitrofluorobenzene Sanger s reagent). 

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