14688-37-0

Upstream product

• 3145-86-6 4-nitrobenzyl iodide 
• 100-11-8 1-bromomethyl-4-nitro-benzene 
• 619-93-2 (Z)-4,4'-dinitrostilbene 
• 555-16-8 4-nitrobenzaldehdye 
• 100-14-1 4-nitrobenzyl chloride 
• 83294-14-8 lithium 2,4-dimethyl-3-nitropentan-3-ide 

Downstream Products

• 968-01-4 (2SR,3SR)-2,3-bis(4-nitrophenyl)oxirane 
• 13295-04-0 1.2-bis(4-nitrophenyl)ethane-1,2-diol 
• 873420-19-0 α'-iodo-4,4'-dinitro-bibenzyl-α-ol 
• 36898-62-1 4,4'-dinitrobenzoin 
• 1033-26-7 4,4'-dinitrobenzophenone 
• 555-16-8 4-nitrobenzaldehdye 
• 57507-54-7 (1S,2R)-2-Methoxy-1,2-bis-(4-nitro-phenyl)-ethanol 
• 619-93-2 4,4'-dinitro stilbene 
• 6067-45-4 4,4'-dinitrobenzil 
• 57507-60-5 2-Methoxy-1,2-bis-(4-nitro-phenyl)-ethanone 
• 736-31-2 trans-4,4'-dinitrostilbene 
• 105222-70-6 α,α'-dichloro-4,4'-dinitro-bibenzyl 

Relevant academic research and scientific papers

Synthesis of Epoxides from Alkyl Bromides and Alcohols with in Situ Generation of Dimethyl Sulfonium Ylide in DMSO Oxidations

Direct conversion of the readily available alkyl bromides and alcohols to value-added epoxides using dimethyl sulfoxide (DMSO) under mild reaction conditions has been developed. Benzyl and allyl bromides, and activated and unactivated alcohols all proceeded smoothly to give epoxides in high to excellent yield. Dimethyl sulfide, generated by DMSO oxidations, was in situ elaborated to form the substituted dimethyl sulfonium ylide species that participates in the Corey-Chaykovsky epoxidation in a domino and one-pot fashion, respectively.

A highly enantioselective one-pot sulfur ylide epoxidation reaction

Enantiomerically pure tricyclic C2-symmetric sulfide 1 can be prepared in high yield and only three steps from D-mannitol. When used in a one-pot sulfur ylide mediated epoxidation reaction, between 94 and 98% enantiomeric excess was obtained; the highest reported to date for the catalytic process. Molecular modelling studies of the ylide conformation provides a basis for understanding the stereochemical outcome of the reaction.

Experimental evidence for multiple oxidation pathways in the (salen)Mn-catalyzed epoxidation of alkenes

The substrate electronic effects on the selectivity in the catalytic epoxidation of para-substituted cis stilbenes 2a-i were investigated by using (R,R)-[N,N′-bis(3,5-di-tBu-salicylidene)-1,2-cyclohexanediamine] manganese(III) chloride 1 in benzene as the catalyst with iodosobenzene as the terminal oxidant. A Hammett study of the selectivity results reveals a stronger electrophilic character than previously assumed in the (salen)Mn-catalyzed reaction. In general, the best correlations with the experimental values were obtained by using the Hammett σ+ values, which gave ρ = -1.37 for the rate of cisepoxide formation and ρ = -0.43 for the rate of the stepwise process leading to the corresponding trans product. The reaction involves two separate pathways as indicated also by the competitive breakdown of the intermediate on the path to trans epoxide for methoxy-substituted substrates. The asynchronicity in the concerted pathway leading to cis epoxide is apparent for 4-methoxy-4′-nitrostilbene, which yields cis epoxide with 75% ee entirely as a result of electronic effects.

Electron-transfer versus Nucleophilic Substitution in the Reactions of α-Halogenated 4-Nitrotoluenes with Base

A comparative study of the reactions of 4-nitrobenzyl and 4-nitrobenzylidene halides (ArCHXY; Ar = 4-NO2C6H4-; X = H or Halogen; Y = Halogen) with alkali shows that the reaction is sensitive to the nature of the side chain halogen substituent(s) as well as the reaction conditions.In alcoholic alkali, only 4-nitrobenzyl chloride (ArCH2Cl) reacts smoothly via the electron transfer (ET)-radical pathway to give mainly dimeric products while the corresponding bromide (ArCH2Br) and iodide (ArCH2I) give exclusively SN products.The ET pathway is enhanced for these substrates by the application of phase-transfer catalysis.In the case of the 4-nitrobenzylidene dihalides (ArCHXY; X = Y = Cl; X = Cl, Y = Br; X = Y = Br; X = F, Y = Br) it is also shown that although progressive bromine substitution suppresses the ET pathway, application of phase-transfer catalysis minimises competing solvolytic reactions and enhances the radical reaction.

Preparation of optically active stilbene oxides via sulfonium salts derived from C2 symmetric thiolanes

Trans-stilbene oxides have been obtained in up to 83% enantiomeric excess via reaction of S-benzyl ylides prepared from optically active trans-2,5-disubstituted thiolanes.

The Correlation of Regiochemistry with Structure in the SRN1 Reaction of aci-Nitronates with p-Nitrobenzylic Substrates

The rate and regiochemistry of the SRN1 reactions of aci-nitronates with p-nitrobenzylic substrates are profoundly affected by branching at the positions adjacent to the reaction sites (Cβ).Definitive rules which predict whether C-alkylation will occur in the association step involving p-nitrobenzylic radicals and aci-nitronate ions are formulated. β-Branching causes O-alkylation or reductive processes to increase.In some cases no recognizable product formation results.Benzylic alcohols, p-nitrophenyl alkyl ketones and/or their oximes, and p-nitrophenol are among the products which result from subsequent reactions of the O-alkylation products, aci-nitronic esters of benzylic alcohols.