94678-96-3

Upstream product

• 487-68-3 mesytaldehyde 
• 707-74-4 (trichloromethyl)mesitylene 
• 1068-57-1 acetic acid hydrazide 
• 110-86-1 pyridine 
• 626-55-1 3-Bromopyridine 
• 52023-52-6 N,N,N',N'-tetraformylhydrazine 
• 108-67-8 1,3,5-trimethyl-benzene 
• 82988-76-9 mesityl diazomethane 
• 121-69-7 N,N-dimethyl-aniline 
• 120-72-9 indole 
• 110-91-8 morpholine 
• 110-89-4 piperidine 
• 93731-78-3 benzenesulfonic acid, 4-methyl-, 2-[(2,4,6-trimethylphenyl)methylene]hydrazide 

Downstream Products

• 487-68-3 mesytaldehyde 
• 2571-52-0 cyanomesitylene 

Relevant academic research and scientific papers

Ruthenium(ii)-catalysed 1,2-selective hydroboration of aldazines

Herein, an efficient and simple catalytic method for the selective and partial reduction of aldazines using ruthenium catalyst [Ru(p-cymene)Cl2]2 (1) has been accomplished. Under mild conditions, aldazines undergo the addition of pinacolborane in the presence of a ruthenium catalyst, which delivered N-boryl-N-benzyl hydrazone products. Notably, the reaction is highly selective, and results in exclusive mono-hydroboration and desymmetrization of symmetrical aldazines. Mechanistic studies indicate the involvement of in situ formed intermediate [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] (1a) in this selective hydroboration.

Orthoamide, LX [1]. N,N,N',N'-Tetraformylhydrazine- a Formylation Agent for Aromatic Compounds of Wide Scope

The reagent system formed from N,N,N',N'-tetraformylhydrazine (3) and aluminum chloride allows the formylation of aromatic compounds. The scope of the method is comparable with the Olah formylation and the Gross-Rieche procedure, since benzene and fluorobenzene can be formylated. Two formyl groups are transferred from 3 to the aromatic nuclei when a molar ratio 4:1:4 (aluminum chloride/3/aromatic compound) is chosen.

A convenient method for the generation of a disulfur monoxide equivalent and its reaction with diazoalkanes to yield dithiirane 1-oxides

Oxidation of elemental sulfur (S8) with dimethyldioxirane (or CF3CO3H) generates a disulfur monoxide equivalent ("S2O"). Yields of "S2O" of 30-40% are obtained from equimolar amounts of S8 and an oxidizing agent. "S2O" reacts with diazoalkanes to give dithiirane 1-oxides [Eq. (1)].

An alternative channel of reductive condensation of trichloromethylarenes with hydrazines

The reductive condensation of trichloromethylarenes with hydrazines can proceed without intermediate formation of pyridinium salts and without participation of pyridine in the reduction act. Variants of reductive condensation using hydrazines as reducting agents and α-chlorobenzylhydrazines and hydrazonoyl chlorides, nitrite imines, or hydrazonoylpyridinium salts as intermediates are considered. α-Chlorobenzylhydrazines and hydrazonoyl chlorides are shown to be the most probable intermediates.

Some reactions of pyridinium salts derived from trichloromethylarenes with N- and C-nucleophiles

The reaction of N-(4-pyridyl)pyridinium and 4-chloropyridinium salts obtained from 1-trichloromethyl-2,4,6-trimethylbenzene and pyridine with N-nucleophiles such as piperidine and morpholine and with C-nucleophiles such as N,N-dimethylaniline and indole proceeds through hetarylation and gives the corresponding 4-substituted pyridines. N-(α,α-Dichlorobenzyl)pyridinium and N,N'-(α-chlorobenzylidene)bispyridinium salts obtained from trichloromethylbenzene do not undergo hetarylation.

NATURE OF THE REDUCING AGENT AND MECHANISM OF THE REDUCTIVE CONDENSATION OF TRICHLOROMETHYLARENES WITH HYDROXYLAMINE AND HYDRAZINES IN PYRIDINE

It was shown that during the reductive condensation of trichloromethylarenes with hydroxylamine or hydrazines in pyridine the event of reduction with replacement of one chlorine atom by a hydrogen atom occurs without the participation of hydroxylamine or hydrazine.The first step of the reaction is the formation of N-(α,α-dichloroarylmethyl)pyridinium chlorides, which are converted by the action of the chloride anion or a second pyridine molecule to the corresponding 4-substituted 1,4-dihydropyridines.The latter undergo further aromatization with transfer of hydrogen from the 4-position of the dihydropyridine ring to the benzyl dichloromethylene group and the formation of N-(α-chloroarylmethyl)-4-chloropyridinium chlorides or N-(α-chloroarylmethyl)-4-(pyridino)pyridinium dichlorides, which give the corresponding aldehydes in hydrolysis or products of reductive condensation under the action of hydroxylamine or hydrazines.

Initial steps in the reductive condensation of trichloromethylarenes with hydroxylamine and hydrazines in pyridine

Data concerning the initial steps in the reductive condensation of trichloromethylarenes with hydroxylamine or hydrazines in pyridine have been obtained.High yields of the products of the reductive condensation obtained even at equimolar ratios of trichloromethylarene with hydroxylamine or hydrazine as well as the formation of unusual products, i.e., 4-pyridylhydrazones of substituted benzaldehydes, have been interpreted as the results of the participation of pyridine in the reaction as a reductive agent. - Key words: trichloromethylarenes, reductive condensation with hydroxylamine or hydrazines, role of pyridine; 4-pyridylhydrazones of substituted benhaldehydes.

Reductive condensation of trichloromethylarenes with hydroxylamine and hydrazines in pyridine

The interaction of trichloromethylarenes with hydroxylamine in pyridine involves the reductive oximation of aryltrichloromethanes. Further transformations of the oximes in the reaction course can result in the formation of nitriles or 3,5-diaryl-1,2,4-oxadiazoles as final products. The conversion depth depends on reaction conditions and structures of trichloromethyl-arenes. When hydrazines used instead of hydroxylamine, respectivebenzaldehyde hydrazones or azines are obtained.