J»-Nitrobenzoyl chloride

There are different methods of the synthetic preparation of acronycine (W. M. Bandaranayake et al., J. Chem. Soc. Perkin 1, 998 (1968) J. Hlubucek et al. Aust. J. Chem. 23, 1881 (1970). One of them is described below. Friedel-Crafts condensation between 2-nitrobenzoyl chloride and 3,5-dimethoxyphenol. 

Methyl /j-(/ /-nitrobenzoylamlno)benzoate 584 A solution of methyl / -aminobenzoate (2.6 g) in methanol-free, dry chloroform (20 ml) is treated with a solution of p-nitrobenzoyl chloride (2.9 g) in chloroform (10 ml), followed by anhydrous pyridine (5 ml). The mixture becomes warm and a pale yellow compound begins to separate. After 15 h at 20° the mixture is filtered. Recrystallization of the solid (4.6 g, 98 %) from ethyl acetate gives the acylamino ester, m.p. 244°. 

A soln. of p-nitrobenzoyl chloride in dry pyridine added dropwise with shaking at 0° to a soln. of benzyl 2,3,4-tri-O-benzyl-D-glucopyranuronate in the same medium, and stored 2-3 days at room temp. benzyl l-O-p-nitrobenzoyl-2,3,4-tri-O-benzyl-D-glucopyranuronate. Y 71%. F. e. and methods s. D. Keglevic, N. Pravdic, and J. Tomasid, Soc. (C) 1968, 511. 

Foussereau J (1989) Accidental occupational sensitization to p-nitrobenzoyl chloride in a chemistry student synthesizing procaine. Contact Dermatitis 20 397-398... 

A 10%-soln. of pentane-2,4-dione copper complex in chloroform shaken 12-24 hrs. at room temp, with a 10%-soln. of m-nitrobenzoyl chloride in the same solvent, and the crude intermediate triketone heated 10-15 min. with aq. 3 N NHg l-m-nitrophenylbutane-l,3-dione. Y 92%.—The method is simple, gives good yields of pure products, and is the most convenient one for the prepn. of certain / -diketones. F. e., also deacetylation of the triketones with ethanolic 30%-H2S04, and condensations with ethyl acetoacetate copper complex, s. W. J. Barry, Soc. 1960, 670. 

Acylpyran-2,4-diones. A mixture of 6-methyl-2H-pyran-2,4 (3H) -dione, m-nitro-benzoyl chloride, and trifluoroacetic acid refluxed 1.5-2 hrs. until HGl-vapors cease to be evolved -> 3-m-nitrobenzoyl-6-methyl-2H-pyran-2,4(3H)-dione. Y 99%. F. e. s. L. L. Woods and P. A. Dix, J. Org. Ghem. 26, 2588 (1961). 

A dry anomeric mixture of 2,3,5-tri-O-benzyl-l-O-p-nitrobenzoyl-D-arabino-furanose added to methylene chloride satd. with anhydrous HCl at 0°, kept 2 hrs. at 0°, the resulting crude chloride dissolved in dry methylene chloride, added to a mixture of dry N-benzoyladenine and Na-zeolite (molecular sieve, Type A4, Fisher Scientific Co.), stirred 1 week at room temp, in a glass-stoppered flask, and the crude product refluxed 5 hrs. with Ba-methoxide in methanol 9-(2,3,5-tri-O-benzyl-j -D-arabinofuranosyl) adenine. Y 46%.— This... 

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