63242-15-9

Upstream product

• 98-88-4 benzoyl chloride 
• 2051-62-9 4'-biphenyl chloride 
• 106-39-8 bromochlorobenzene 
• 1137-42-4 4-Hydroxybenzophenone 
• 1679-18-1 4-Chlorophenylboronic acid 
• 134-85-0 4-chlorobenzophenone 

Downstream Products

• 63242-36-4 4'-Chloro-4-(chloro-phenyl-methyl)-biphenyl 

Relevant academic research and scientific papers

Pd-Catalysed Suzuki-Miyaura cross-coupling of aryl chlorides at low catalyst loadings in water for the synthesis of industrially important fungicides

The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed running the reaction with 50 ppm of Pd-catalyst loading without an additional organic solvent in the cross-coupling reaction step in short reaction times. The system was optimised for the initial cross-coupling step of the large scale produced fungicides Boscalid, Fluxapyroxad and Bixafen up to 97% yield. It is also shown that the Suzuki-Miyaura reaction can be easily scaled up to 50 g using a simple product separation and purification using environmentally benign solvents in the work-up. To show the usability of this method, it was additionally applied in the three-step synthesis of the desired active ingredients.

The Barbier-Grignard-Type Arylation of Ketones and Unexpected Cross-Coupling of Phenolic Ketones using Unactivated Aryl Bromides

A novel, highly versatile and efficient method has been developed for the Barbier-Grignard-type arylation of ketones and an unexpected cross-coupling of phenolic ketones was observed using unactivated bromides and magnesium in tetrahydrofuran/toluene at 96°C promoted by multicatalysts of cupric bromide (15 mol%), bismuth chloride (5 mol%) and silver bromide (10 mol%). The substituent and electronic effects on the reaction have been discussed. High yields of arylation and cross-coupling have been attained under mild conditions. A novel reasonable mechanism involving a quinone intermediate is proposed. The high chemical selectivity in the cross-coupling to the hydroxy group of phenolic ketones should help ketones find new applications.