24459-52-7

Upstream product

• 104-87-0 4-methyl-benzaldehyde 
• 57-14-7 N,N-Dimethylhydrazine 
• 66064-57-1 (E)-1,1-dimethyl-2-(2-methylallylidene)hydrazine 
• 200280-07-5 C₁₆H₁₇N 
• 104-94-9 4-methoxy-aniline 
• 62-53-3 aniline 
• 95-68-1 2,4-Xylidine 
• 10272-07-8 3.5-dimethoxyaniline 
• 7559-36-6 4-methyl-β-nitrostyrene 

Downstream Products

• 104-85-8 para-methylbenzonitrile 
• 120779-86-4 Ethyl 3-(p-tolyl)-3-dimethylhydrazono-2-oxopropionate 
• 120779-91-1 ethyl 1-methyl-3-(p-tolyl)-1H-pyrazole-4-carboxylate 
• 104-87-0 4-methyl-benzaldehyde 
• 111269-40-0 3-(p-tolyl)-1,1,1-trifluoropropane-2,3-dione 3-dimethylhydrazone 
• 256934-09-5 (3-methoxy-2-p-tolyl-2,5-dihydro-pyrrol-1-yl)-dimethyl-amine 
• 99-94-5 p-Toluic acid 
• 619-55-6 para-methylbenzamide 
• 161643-63-6 3,3,3-Trifluoro-2,2-dihydroxy-1-p-tolyl-propan-1-one 
• 161643-97-6 1,1,1-Trifluoro-3-hydrazono-3-p-tolyl-propan-2-one 
• 121194-22-7 Methyl-((E)-3,3,3-trifluoro-1-p-tolyl-propenyl)-diazene 
• 130799-72-3 N,N,N-Trimethyl-N'-[1-p-tolyl-meth-(E)-ylidene]-hydrazinium; iodide 
• 121194-34-1 3,3,3-trifluoro-1-(4-methylphenyl)propan-1-one 

Relevant academic research and scientific papers

Mechanistic Studies on the Michael Addition of Amines and Hydrazines to Nitrostyrenes: Nitroalkane Elimination via a Retro-aza-Henry-Type Process

In this article we report on the mechanistic studies of the Michael addition of amines and hydrazines to nitrostyrenes. Under the present conditions, the corresponding N-alkyl/aryl substituted benzyl imines and N-methyl/phenyl substituted benzyl hydrazones were observed via a retro-aza-Henry-type process. By combining organic synthesis and characterization experiments with computational chemistry calculations, we reveal that this reaction proceeds via a protic solvent-mediated mechanism. Experiments in deuterated methanol CD3OD reveal the synthesis and isolation of the corresponding deuterated intermediated Michael adduct, results that support the proposed slovent-mediated pathway. From the synthetic point of view, the reaction occurs under mild, noncatalytic conditions and can be used as a useful platform to yield the biologically important N-methyl pyrazoles in a one-pot manner, simple starting with the corresponding nitrostyrenes and the methylhydrazine.

Visible-Light Photoredox-Catalyzed C-H Difluoroalkylation of Hydrazones through an Aminyl Radical/Polar Mechanism

An unprecedented visible-light-induced direct C-H bond difluoroalkylation of aldehyde-derived hydrazones was developed. This reaction represents a new way to synthesize substituted hydrazones. The salient features of this reaction include difluorinated hy

Gold-Catalyzed Highly Selective Photoredox C(sp2)-H Difluoroalkylation and Perfluoroalkylation of Hydrazones

The first gold-catalyzed photoredox C(sp2)-H difluoroalkylation and perfluoroalkylation of hydrazones with readily available RF-Br reagents is reported. The resulting gem-difluoromethylated and perfluoroalkylated hydrazones are highl

A Single Electron Transfer (SET) Approach to C-H Amidation of Hydrazones via Visible-Light Photoredox Catalysis

The reductive single electron transfer (SET) umpolung amination of aldehyde-derived hydrazones has been developed through visible-light-promoted photoredox catalysis. The ideal transformation of hydrazones into the corresponding hydrazonamide through selective carbon-hydrogen (C-H) bond functionalization represents one of the most step- and atom-economical methods. This SET umpolung strategy features mild conditions and a remarkably broad substrate scope, offering an entirely new substrate class to direct C-H amination.

New types of reactivity of α,β-unsaturated N,N- dimethylhydrazones: Chemodivergent diastereoselective synthesis of functionalized tetrahydroquinolines and hexahydropyrrolo[3,2-b]indoles

The indium trichloride-catalyzed reaction between aromatic imines and α,β-unsaturated N,N-dimethylhydrazones in acetonitrile afforded 1,2,3,4-tetrahydroquinolines bearing a hydrazone function at C4 through a one-pot diastereoselective domino process that involves the formation of two C-C bonds and the controlled generation of two stereocenters, one of which is quaternary. This reaction constitutes the first example of an α,β-unsaturated dimethylhydrazone that behaves as a dienophile in a hetero Diels-Alder reaction. The related reaction between anilines, aromatic aldehydes, and methacrolein dimethylhydrazone in CHCl3 with BF 3·Et2O as catalyst afforded polysubstituted 1,2,3,3a,4,8b-hexahydropyrrolo[3,2-b]indoles as major products through a fully diastereoselective ABB′C four-component domino process that generates two cycles, three stereocenters, two C-C bonds, and two C-N bonds in a single operation. Copyright

Reaction of the lithio-derivative of methoxyallene with hydrazones. Part 1: Synthesis and transformation of α-allenyl hydrazines

The lithio-derivative of methoxyallene reacts with aldehyde hydrazones leading to expected α-allenyl hydrazines when ether is the solvent of the reaction. The yields are good as well as the diastereoselectivity observed in the case of SAMP-hydrazones. These hydrazines are cleanly transformed to N-dialkylamino-3-methoxy-3-pyrrolines when they are reacted with n-BuLi in THF. These compounds are sometimes accompanied by the isomeric 4-methyl azetidines. The N-dialkylamino-3-methoxy-3-pyrrolines are transformed to 3-methoxy-3-pyrrolines by hydrogenolysis of the nitrogen-nitrogen bond, to 3-alkoxy-pyrroles by treatment with a peracid and to 3-amino-pyrroles by acidic migration of the dialkylamino group. In the case of SAMP-hydrazines, the obtained 3-methoxy-3-pyrrolines have a high enantiomeric purity. Lastly, attempts to prepare α-hydrazino-esters (and subsequently α-amino-esters) by ozonolysis of the allenyl moiety failed due to the formation of a methyl glyoxylate.

A facile synthesis of 3-alkoxy and 3-amino pyrroles

N-Amino-3-methoxy-3-pyrrolines 2 obtained from the reaction of 1-lithio methoxyallene with arylhydrazones may be converted to either 3-methoxy pyrroles 6 or 3-amino pyrroles 7 by treatment with m-chloroperbenzoic acid or 0.25 M HCl, respectively.

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.