138616-24-7

Upstream product

• 555-16-8 4-nitrobenzaldehdye 
• 57-14-7 N,N-Dimethylhydrazine 

Downstream Products

• 121194-30-7 Methyl-[(E)-3,3,3-trifluoro-1-(4-nitro-phenyl)-propenyl]-diazene 
• 721-68-6 3,3,3-trifluoro-1-(4-nitrophenyl)propan-1-one 
• 76847-63-7 acetic acid N',N'-dimethyl-N-(4-nitro-benzyl)-hydrazide 
• 41159-02-8 2-(4-nitrophenyl)-1,3-dithiolane 
• 130799-77-8 N,N,N-Trimethyl-N'-[1-(4-nitro-phenyl)-meth-(E)-ylidene]-hydrazinium; iodide 
• 619-72-7 4-nitrobenzonitrile 

Relevant academic research and scientific papers

Conversion of Aldehydes into Nitriles via Oxidation of Their Dimethylhydrazones

The 3-chloroperoxybenzoic acid oxidation of dimethylhydrazones of aromatic aldehydes gives the corresponding nitriles in good yields.Two further examples of the same oxidative transformation of cinnamaldehyde and of hexanal are also given.Except for hexanal hydrazone, all other aldehyde hydrazones can also be efficiently converted into nitriles by treatment with methanolic 30percent hydrogen peroxide in the presence of catalytic amounts of selenium dioxide or, preferentially, 2-nitrobenzeneseleninic acid.

Copper-catalyzed trifluoromethylation of N,N-dialkylhydrazones

Mild and practical: Trifluoromethylation of (hetero)aromatic aldehyde N,N-dialkylhydrazones was achieved at room temperature by using Togni's trifluoromethylation reagent under CuCl catalysis (see scheme). This simple reaction is believed to occur by a CF3-radical-transfer mechanism and yields useful trifluoromethylated building blocks. Copyright

Photoisomerisation of (E)- to (Z)-N,N-Dimethylhydrazones and Thermal Reversion

The E-isomers of aliphatic aldehyde N,N-dimethylhydrazones undergo competing E to Z isomerisation and photolysis to nitriles under UV (254 nm) irradiation.The Z-E isomer mixture which results thermally reverts to the more stable E-Isomer and under short irradiation times the photoisomerisation/thermal reversion cycle can be reversible.Trimethylacetaldehyde N,N-dimethylhydrazone undergoes similar reactions (ruling out the intervention of other types of hydrazone isomerisation) and the rates of the thermal Z->E reactions for RCH=N-NMe2 are in the order R = But > Et > Me.The results are considered in terms of conformations of the hydrazones and the mechanism of E-Z isomerisation.

Elimination Reactions of Hydrazonium Salts: Experimental and Theoretical Evidence for a Large Stereoelectronic Effect of Nitrogen

Elimination of trimethylamine from hydrazonium salts (8, R = Me) is promoted by base (methoxide ion in methanol).The mechanism is characterized as E2 as shown by substituent effects (ρ = +2.57), Broensted coefficients, a primary kinetic isotope effect (kH/kD = 2.10), and solvent effects.Variation in the leaving group (8, R = arylmethyl) shows that N-N bond cleavage is less well advanced in the transition state than C-H bond breaking.The elimination to give the nitrile is syn-periplanar and, using the phthalazinium salt 4 as a model for the anti elimination, an anti/syn ratio of ca. 102 is found.The reactions have been modelled using ab initio methods with the transition structures located at the HF/3-21G level and relative energies computed using the MP2/6-31G* method.Using both H2O and NH3 as model bases to induce elimination on +, the calculated energy for anti elimination is lower (in the range 11-13 kcal mol-1) than that for syn elimination.The implications of the results for the ease of formation of nitriles from aldehydes via the hydrazonium salt route are discussed.