182684-65-7

Upstream product

• 5670-69-9 1,1'-(2-nitroethene-1,1-diyl)dibenzene 
• 6921-34-2 benzylmagnesium chloride 
• 182684-54-4 2,2,3-triphenylpropanohydroximoyl chloride 
• 202061-27-6 1-nitro-2,2,3-triphenylpropane 

Relevant academic research and scientific papers

Generation of nitroalkanes, hydroximoyl halides and nitrile oxides from the reactions of β-nitrostyrenes with Grignard or organolithium reagents

The β-nitrostyrenes 1 or 2 react with Grignard or organolithium reagents in ether or THF solution to generate by 1,4-addition the intermediate nitronates A. When A is treated with dilute hydrochloric acid, high yields of the nitroalkanes 3 (and oximes 4) or 5 are obtained Hydroximoyl halides 6, 8 or nitrile oxides 7 can be isolated when the intermediate A is slowly added to the ice cold concentrated hydrohalic acid. The same products 6 and/or 7 are observed if the nitronates, generated from the substrate 1a, are added to 85% aqueous H2SO4 but only the hydrolyzed carboxylic acids 9 are generated when the β-nitrostyrenes 2 are reacted with Grignard reagents and worked up under the same condition. The nitrile oxides 7 can undergo 1,3-dipolar cycloaddition with alkenes or alkynes to generate 2-isoxazolines or isoxazoles. A one-pot synthesis of the [n,3,0] bicyclic (n = 3 or 4) compounds 23-27 by intramolecular nitrile oxide-olefin cycloadditions is reported.

Reactions of β-nitrostyrenes with Grignard reagents

α-Phenyl-β-nitrostyrene 1a and β-nitrostyrene 1b react with Grignard reagents to generate hydroxyimoyl halides 3 or nitrile oxides 4 after workup with ice cold concentrated aqueous HX acid solution. Carboxylic acids 5 are the only products isolated from 1b and products 3 or 4 are still obtained from 1a when concentrated sulfuric acid solution is used.