121034-79-5

Upstream product

• 55165-45-2 2-cyano-benzenediazonium tetrafluoroborate 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 1885-29-6 anthranilic acid nitrile 
• 2042-37-7 o-cyanobromobenzene 
• 4387-36-4 2-iodobenzonitrile 
• 38622-91-2 [(p-methylphenyl)sulfonylmethyl]isonitrile 
• 98-59-9 p-toluenesulfonyl chloride 
• 143-33-9 sodium cyanide 

Relevant academic research and scientific papers

TosMIC and its derivatives as versatile sulfonylating agents for the synthesis of p-toluenesulfonylarenes from aryl halides and arylboronic acids

An efficient copper(II) catalyzed sulfonyation of aryl halides has been achieved using TosMIC (p-toluenesulfonylmethyl isocyanide) as a sulfonylating agent. This newly developed sulfonylation approach provides an easy access for the synthesis of diaryl sulfones from aryl bromides, iodides and boronic acids with TosMIC under neutral conditions. This method is useful for the sulfonylation of aryl boronic acids under similar conditions. This is the first report on the sulfonylation of aryl bromides, iodides and boronic acids using TosMIC.

Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones

We disclose herein the first transition-metal-and external oxidant/reductant-free visible-light-mediated synthesis of (un)symmetrical diaryl/alkyl aryl sulfones from arenediazonium tetrafluoroborates and sodium sulfinates using eosin Y as an organic photoredox catalyst. The utilization of visible light as an inexpensive and ecosustainable energy source, operational simplicity, ambient temperature and clean reaction in aqueous acetonitrile are the salient features of the developed protocol. The desired sulfones were also synthesized via a one-pot, two-step process directly from anilines and sulfinate salts in good to excellent yields.

Visible-light-driven electron donor-acceptor complex induced sulfonylation of diazonium salts with sulfinates

This work reports an efficient sulfonylation reaction enabled by a visible-light-induced radical coupling reaction between phenyl/heterocyclic diazonium salts and sulfinates. Mechanistic experiments disclosed the formation of a versatile electron donor-acceptor (EDA) complex. This transformation is characterized by an easy operational procedure under mild conditions which avoids transition metals, ligands, catalysts, and oxidants.

Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis

An efficient visible-light-assisted, copper-catalyzed sulfonylation of aryl halides with sulfinates is reported. In our protocol, a single ligand CuI photocatalyst formed in situ was used in the photocatalytic transformation. Diverse organosulfones were obtained in moderate to good yields. This strategy demonstrates a promising approach toward the synthesis of diverse and useful organosulfones.

A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides

A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).

Nucleophilic addition and substitution reactions between the cyanide ion and cyclopentadienyliron complexes of chlorobenzenes. Synthesis of benzonitriles and phthalonitriles

Reaction of cyclopentadienyliron (CpFe) complexes of chlorobenzenes with NaCN in DMF could give risemto products resulting from the addition of the cyanide ion or from substitution and addition reactions with the cyanide ion.Demetallation-oxidation of such products by treatment with DDQ would lead to the synthesis of benzonitriles and phthalonitriles.With the CpFe complex of chlorobenzene, reaction with NaCN in DMF for 3 min, 30 min, or 3 h gave rise to an approximately 90:10 mixture of (1-5-η5-1-chloro-exo-6-cyanocyclohexadienyl)(η5-cyclopentadienyl)iron (9) and (1-5-η5-1-exo-6-dicyanocyclohexadienyl)(η5-cyclopentadienyl)iron (10), a 40:60 mixture of 9 and 10 or pure 10, respectively.When the 3-h reaction was worked up in the presence of an added aqueous solution of NH4PF6, only the substitution product, the (η6-benzonitrile)(η5-cyclopentadienyl)iron cation (11), was obtained as its hexafluorophosphate.Apparently, under the acidic conditions of the added aqueous NH4PF6, 10 could readily revert to 11 which gave rise to its hexafluorophosphate.DDQ treatment of the 3-min or 3-h reaction product gave, respectively, o-chlorobenzonitrile or phthalonitrile.Similary reaction of CpFe complexes of o-substituted chlorobenzenes could give rise to CpFe-complexed cyclohexadienyl systems two cyano groups,at the 1- and 6-positions and the original o-substituent at the 2-position.DDQ treatment of such products would lead to the of 3-substituted phthalonitriles, and in the present work, 3-methyl, 3-methoxy-, and 3-phenoxyphthalonitriles were prepared in this way.In another set of reactions, depending on the experimental conditions employed, the CpFe complex of 2,6-dichlorotoluene (20) could give products from cyanide addition only, the DDQ treatment of which lead to the formation of 2,4-dichloro-3-methylbenzonitrile, or products from substitution and addition and subsequent DDQ treatment of which give rise to 4-chloro-3-methylphthalonitrile.Keywords: η6-chlorobenzene-η5-cyclopentadienyliron cation, complexed chlorobenzenes, nucleophilic addition of cyanide ion, nucleophilic substitution with cyanide ion, synthesis of benzonitriles and phthalonitriles.