3236-92-8Relevant academic research and scientific papers
Synchronous double C-N bond formation via C-H activation for a novel synthetic route to phenazine
Seth, Kapileswar,Raha Roy, Sudipta,Chakraborti, Asit K.
supporting information, p. 922 - 925 (2016/01/16)
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
Seth, Kapileswar,Roy, Sudipta Raha,Kumar, Asim,Chakraborti, Asit K.
, p. 2892 - 2896 (2016/05/24)
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.
Acetamidinosulphenylation of Alkynes via Electrophilic Addition of 4'-Substituted Benzenesulphenanilides in Acetonitrile
Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 1105 - 1111 (2007/10/02)
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.
BORON TRIFLUORIDE PROMOTED REACTION OF BENZENESULPHENANILIDES WITH ALKENES
Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 1145 - 1156 (2007/10/02)
The boron trifluoride-promoted reaction of a series of 3'- and 4'-substituted benzenesulphenanilides (1) with various alkenes has been investigated as a potential synthetic route to arylaminosulphides.The benzenesulphenanilides (1) investigated generally afford arylaminosulphenylation adducts in fair to good yields except for the methoxy-substituted anilides (1e and f), which largely lead to decomposition products under comparable conditions.In all cases examined, the addition proceeds with trans-stereospecificity and, with terminal alkenes, leads regioselectively to the exclusive (or predominant) formation of the terminal sulphides.The findings are interpreted by assuming that boron trifluoride transforms the sluggish benzenesulphenanilides (1) into reactive electrophilic species, which can undergo nucleophilic attack at sulphur by an alkene, presumably affording episulphonium-borate ion-pair intermediates, in competition with attack by another sulphenanilide unit.
Acid-promoted Decomposition of Benzenesulphenanilides and N-Aryl Bis(benzenesulphen)amides
Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
, p. 2261 - 2266 (2007/10/02)
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).
