53890-65-6

Upstream product

• 1610-26-0 1-nitro-4-(nitromethyl)benzene 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 1011-84-3 4-nitrobenzohydroximoyl chloride 
• 19279-27-7 5-(4-nitro-phenyl)-[1,3,2,4]dioxathiazole 2-oxide 
• 1829-60-3 dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate 
• 2574-03-0 p-nitrobenzonitrile oxide 
• 947-57-9 dimethyl bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate 
• 19019-88-6 7-isopropylidene-2,3-dicarbomethoxynorbornadiene 

Relevant academic research and scientific papers

SITE SELECTIVITY IN THE REACTIONS OF 1,3-DIPOLES WITH NORBORNADIENE DERIVATIVES

The cycloadditions of arylazides, benzonitrile oxides and diphenylnitrile imine to norbornadiene derivatives 1a-c showed varying degree of site- and stereo-selectivity.With dipolarophile 1a arylazides and benzonitrile oxides attack, preferentially, the electron-poor tetrasubstituted double bond, while in the case of 1b and 1c is the substituted double bond which enters the cycloaddition.By contrast, 2-diazopropane and C-phenyl-N-methylnitrone react with the sole tetrasubstituted double bond of 1a-c in stereo- and site-specific cycloadditions.The quantitative evaluation of the two possible reaction paths was performed by glc analysis.The compounds detected were those arising from Diels-Alder cycloreversions of the thermally labile intermediate adducts 2 and 3 (Scheme 1).The results were rationalized on the basis of a qualitative perturbation treatment which considers frontier orbital interactions only.

An investigation of the reaction of primary nitroalkanes with acetic anhydride/sodium acetate

Oxidation of primary nitroalkanes by acetic anhydride/sodium acetate has been found to be more complex than previously suspected. Phenylnitromethane, with acetic anhydride/sodium acetate at 60-80°, for example, gives a mixture of benzoic anhydride, triacethylhydroxylamine and acetanilide, through the mixed anhydride {A figure is presented} as a key intermediate. Evidence in support of this latter species has been obtained by carrying out the oxidation in the presence of dimethyl acetylenedicarboxylate as a 1,3-dipolarophile, when 3-phenyl-4,5-dicarbomethoxyisoxazole is formed in 82% yield. A number of other 3-alkyl- and 3-aryl-4,5-dicarbomethoxyisoxazoles have been prepared in a similar manner.