127703-35-9

Upstream product

• 132555-11-4 (E)-(4-Cyanophenyl)azo phenyl sulfide 
• 108-95-2 phenol 
• 29577-88-6 (Z)-tert-Butyl (4-cyanophenyl)azo sulfide 
• 111278-47-8 C₁₃H₉N₃S 
• 16909-23-2 tetra-n-butylammonium phenolate 
• 623-03-0 4-Cyanochlorobenzene 
• 139-02-6 sodium phenoxide 
• 3096-81-9 4-phenoxybenzonitrile 

Relevant academic research and scientific papers

A new cascade radical reaction for the synthesis of biaryls and triaryls from benzyl iodoaryl ethers

The paper describes a new method of synthesizing biaryls and triaryls through an intramolecular ipso-substitution reaction initiated by the addition of an aryl radical to a benzyl ether. A tandem variant of the reaction has also been demonstrated. A short synthesis of isoaucuparin 27, a natural product found in the sapwood tissue of Sorbus aucuparia, is also described.

Mechanisms of the photochemical rearrangement of diphenyl ethers

The mechanism of the photochemical rearrangement of diphenyl ether (1a) was studied. Irradiation of 1a in ethanol gave 2-phenylphenol (2, 42%) and 4-phenylphenol (3, 11%) as rearrangement products, in addition to phenol (4, 30%) and benzene (5, 25%) as diffusion products. Cross-coupling experiments employing [2H10]1a demonstrated that the formation of 2- and 4-phenylphenol was an intramolecular process. Irradiation of 1a in benzene or in toluene gave biphenyls in good yields. The combined yields of rearrangement products (2 and 3) increased with increase of solvent viscosity, with a concomitant decrease in the formation of 4. All the results can be rationalized in terms of excitation of 1a to the singlet state and dissociation to a radical pair intermediate involving phenoxy and phenyl radicals. Intramolecular recombination of these radicals gives rearrangement products, and escape followed by hydrogen abstraction from the solvent gives diffusion products. When position 4 of 1a was occupied by an electron-donating substituent (1b-e), aryloxy-phenyl bond cleavage to give the corresponding rearrangement products prevailed over phenoxy-aryl bond cleavage. The opposite was the case for substrates with an electron-withdrawing substituent at position 4 (1h,i).

SRN1C-arylation of potassium aryloxides by arylazo phenyl or tert- butyl sulfides in DMSO

Aryloxide ions (Ar′O-) behave as C-nucleophiles towards diazosulfides (ArN = NSR; R = Ph, But) leading to imsymmetrical hydroxybiaryls (ArAr′OH) via C-C coupling. The reaction is particularly suited for the synthesis of terms which contain electron-withdrawing groups on the Ar moiety. The SRN1 mechanism is proposed on the grounds of experimental evidences.

UNSYMMETRICAL BIARYLS FROM ARYLOXIDE ANIONS AND ARYLAZO PHENYL SULFIDES IN DMSO.

Carbon-arylation of phenoxide and naphthoxide anions by arylazo phenyl sulfides represents a convenient synthesis of unsymmetrically substituted hydroxybiaryls.

Electrochemically Catalyzed Aromatic Nucleophilic Substitution. Phenoxide Ion as Nucleophile

Cyclic voltammetry and preparative-scale electrolysis of aryl halides in the presence of phenoxide ions, a nucleophile reputed as unreactive SRN1 reactions, show the formation, in liquid ammonia or in dimethyl sulfoxide, of coupling products along an electrochemically catalyzed SRN1 aromatic substitution process.Coupling occurs at carbons of the phenyl ring rather than at the phenolic oxygen.The mechanism of the reaction is estabilished on kinetic grounds.Determination of the coupling rate constant between phenoxide ions and aryl radicals and comparison with other n ucleophiles shows that phenoxide ions are quite efficient nucleophiles in SRN1 reactions.The reaction can as well be viewed as an homolytic aromatic substitution.Mechanistic implications concerning the latter type of reaction are discussed.With mediated electrochemical induction of the substitution reaction, it is possible to raise the yield in coupling product up to about 80percent, which renders the reaction an attractive route to the synthesis of electron donor-electron acceptor biaryls.