5051-19-4

Upstream product

• 2101-87-3 p-methoxy-phenylazide 
• 63235-31-4 benzenesulfenic acid p-anisidide 
• 110228-48-3 4'-methoxybiphenyl-2-sulphenanilide 
• 85695-73-4 N-(p-methoxyphenyl)bis(benzenesulphen)amide 
• 503-17-3 dimethylacetylene 
• 75-05-8 acetonitrile 
• 4997-95-9 2-nitro-benzenesulfenic acid-(4-methoxy-anilide) 
• 100-17-4 para-methoxynitrobenzene 
• 51-66-1 4-methoxyacetanilide 
• 536-90-3 m-Anisidine 
• 104-94-9 4-methoxy-aniline 
• 85695-75-6 4-methoxy-N²-(4-methoxyphenyl)-N¹N²-bis(2-nitrophenylthio)-o-phenylenediamine 

Downstream Products

• 24890-66-2 5,10-dioxy-phenazine-2,7-diol 

Relevant academic research and scientific papers

Synchronous double C-N bond formation via C-H activation for a novel synthetic route to phenazine

A novel synthetic strategy for phenazine formation is reported following self-coupling of anilines by Pd-Ag binary nanocluster-catalysed synchronous double C-N bond formation via non-radical mode of ortho-aryl C-H activation.

The palladium and copper contrast: A twist to products of different chemotypes and altered mechanistic pathways

A novel contrast in palladium and copper catalysis is revealed to form products of different chemotypes resulting in a phenazine to azoarene twist through an altered mechanistic pathway (from non-radical C-H activation mode of C-N coupling to radical N-N coupling) during the oxidative self-coupling of anilines catalysed by Pd-Ag and Cu-Ag nanoclusters.

Water at elevated temperatures (WET): Reactant, catalyst, and solvent in the selective hydrolysis of protecting groups

Water at elevated temperatures (WET) can act simultaneously as reactant, solvent, and catalyst in reaction processes. WET has been successfully employed in the removal of protecting groups alleviating the need for added strong acids/bases, subsequent neutralization and waste salt elimination. The protocols for the water-mediated removal of several common protecting groups such as tert-butyl carbamates (N-Boc) from 125 to 150 °C, acetamide (N-Ac) at 275 °C and acetate esters (O-Ac) at 250 °C are reported for different model aryl compounds. In addition, high yields and selective deprotection of one protecting group in the presence of another by simply tuning the temperature is demonstrated. In order to gain further insights into reaction processes, the aqueous solubilities of several of the reactants, the kinetics and mechanisms associated with some of these reactions are also discussed. the Partner Organisations 2014.

Unexpected reactivity between aromatic nitro compounds and PCl3/AlCl3. A new one-pot synthesis of phenazines

The reaction between 4-nitroalkoxybenzenes 7 and PCl3/AlCl3, when carried out in appropriate molar ratio, gives a prevalent formation of diazenes 8 and 2,7-dialkoxyphenazines 9 with their new chlorinated derivatives 10-13. These compounds are obtained, in satisfactory yield, in a one-pot procedure, in mild conditions, from commercially available and safe starting materials. In this reaction both the reagents PCl3 and AlCl3 play a fundamental role in obtaining the products, and this method might be applicable to other 4-alkoxynitrobenzenes.

LDA-promoted decomposition of benzenesulfenamides. A route to aminyl radicals by dioxygen oxidation of lithium amides

The LDA-promoted decomposition of N-monosubstituted sulfenamides 1a-d occurs through the formation of thioaminyl anions, which undergo oxidation either at sulfur, with formation of sulfonamides, or at nitrogen, with formation of thioaminyl radicals, depending on the nature of the 4'-substituent. The reaction of N,N-disubstituted sulfenamides 1e-h proceeds through the intermediacy of a lithium complex capable of generating aminyl radicals via sulfenyl group transfer to the di-iso-propylamido anion and subsequent aerial oxidation of the resulting lithium amides 3e-h.

Acetamidinosulphenylation of Alkynes via Electrophilic Addition of 4'-Substituted Benzenesulphenanilides in Acetonitrile

A number of 4'-substituted benzenesulphenanilides and N-methyl-4'-nitrobenzenesulphenanilide are shown to add to simple alkynes in acetonitrile in the presence of boron trifluoride-diethyl ether to give acetamidinovinyl sulphides in varying yields.Addition is largely favoured by dialkyl substitution on the alkyne and by electron-attracting anilide substituents.Moreover, the azasulphenylation adducts are produced with trans stereospecificity and high regioselectivity (Markovnikov orientation).A likely mechanism involves nucleophilic displacement by the alkyne at the activated sulphur of the anilide complexed with boron trifluoride leading to the initial formation of a thiirenium ion intermediate.Subsequent back-side attack of acetonitrile on the thiirenium ion gives a nitrilium ion which is ultimately trapped by the liberated arylamine.

Intermolecular Thermal Reaction of Arylnitrenes with Furans

4-Methoxy-, 4-chloro-, and 4-nitro-phenylnitrenes have been thermally generated by decomposition of the corresponding aryl azides in the presence of furan and a series of 2-substituted and 2,5-disubstituted furans. 4-Nitrophenylnitrene has been shown to be capable of undergoing electrophilic addition to the furan ring both at the α- and β-position, whereas only evidence of α-attack has been provided by 4-chlorophenylnitrene.On the other hand, no evidence of electrophilic attack has been obtained with 4-methoxyphenylnitrene, which affords only products ascribable to the triplet nitrene.The formation of a number of products ultimately resulting from nitrene attack at the α-position of the furan ring followed by a ring-opening process and the general occurrence of 1-(4-nitrophenyl)- and 1-(4-chlorophenyl)-1,2,3-triazole from thermolysis of 4-nitro- or 4-chloro-phenyl azide in the presence of the furans examined is discussed.

THERMAL REACTIVITY OF 4'SUBSTITUTED- AND 4'-SUBSTITUTED-2-PHENYL-BENZENESUPHENANILIDES

The thermal decomposition of 4'-nitro, 4'-H, and 4'-methoxy-benzenesulphenanilides in benzene and/or furan, and of 4'-substituted-2-phenylbenzenesulphenanilides ( 1d-1f ) in benzene, was found to proceed by two distinct pathways: ( i ) nucleophilic displacement by furan and/or another sulphenanilide unit and ( ii ) homolytic S-N bond fission to give sulphenyl and anilino radicals.An increase in the electron-withdrawning capability of the 4'-substituted favours the ionic pathway, whwreas the radical pathway is favoured by an increase in the reaction temperature.

Acid-promoted Decomposition of Benzenesulphenanilides and N-Aryl Bis(benzenesulphen)amides

The decomposition of 4'-substituted benzenesulphanilides (1a-d) in the presence of trifluoroacetic acid (0.6 equiv.) leads to N-arylbis(benzenesulphen)amides (6a-d) in variable yields, depending on the 4'-substituent, in addition to disulphide (4) and anilines (3a-d), whereas products arising from sulphenylation of the N-aryl ring result from 3'-methoxybenzenesulphenanilide (1g).The 4'-nitro- and 3'-nitro-benzenesulphenanilides (1e,f) react with a slight excess of trifluoroacetic acid to give only (4), the thiosulphonate (5), and aniline (3e,f).The findings are interpreted in terms of possible nucleophilic attack at the S-N bond of a protonated sulphenanilide by the nitrogen or the N-aryl ring of another sulphenanilide unit, according to the nature of the substituent and its position, with displacement of aniline (3).The reaction of (1a-d) with 1.5 equiv. of trifluoroacetic acid leads to complete disappearance of the initially formed amides (6a-d) with concomitant formation of phenazines (9) and/or p-quinone di-imines (8).Similar results are obtained by using boron trifluoride-diethyl ether.Di-imines (8) and phenazines (9) are explained on the basis of a mechanism initially involving nucleophilic attack by (1) and/or (6) and/or (3) at the ortho and para positions of an intermediate cation, possibly (18A) or (18B), and loss of the disulphide (4).

Benzenesulphenanilidyl Radicals. Part 3. Reactions of 4'-Substituted Benzenesulphenanilides with t-Butoxyl Radicals

Decomposition products of the 4'-substituted benzenesulphenanilidyl radicals (2a, b, d, and e), generated from the corresponding benzenesulphenanilides (1) with t-butoxyl radicals, have been investigated in benzene, acetonitrile, and acetone.Results indicate that the decomposition modes exhibited by these radicals are not essentially influenced by variation of the solvent polarity; comparison of the findings with present and previous results from oxidation of (1) with lead dioxide show that the chemical reactivity trend displaced by the thioaminyls (2) can be greatlyinfluenced both by the reaction medium and the 4'-substituent.Evidence is presented that the benzenesulphenanilides (1b) and (1e) react in acetone in the presence of di-t-butyl hyponitrite to give products ascribable to homolytic substitution at the sulphenanilide sulphur by acetonyl radicals.