A green synthesis approach toward large-scale production of benzalacetone via Claisen-Schmidt condensation

Claisen-Schmidt (CS) condensation between acetone and benzaldehyde with NaOH as the catalyst is a well-recognized pathway for the synthesis of benzalacetone (BA). However, this process is compromised by a side reaction, i.e., a second CS reaction between benzaldehyde and the BA product. In this work, we designed a stirring-induced emulsion synthesis technique for the cyclic and scaling-up production of BA with 99 ± 1% selectivity, without the use of surfactants. In this approach, the water-soluble acetone and NaOH were separated from the oil-soluble benzaldehyde by the organic-aqueous phase interface, such that the CS condensation could only be executed at the liquid interface. The just-formed BA molecules diffuse to the interior of the oil solvent, where any subsequent CS post-reaction is rendered negligible, owing to the absence of NaOH. The oil phase containing the BA molecules can be easily separated from the aqueous solution by stopping stirring and undisturbed standing, allowing for a large-scale production protocol. As a proof of concept, over 1 kg of BA was produced in the laboratory with high yield and purity.</p

Enhanced support effects in single-atom copper-incorporated carbon nitride for photocatalytic suzuki cross-coupling reactions

Conditioning the nature of metal active sites for better performance by well designing and constructing the support material is always appealing in heterogeneous catalysis. Herein, Cu species was introduced into the bulk phase of carbon nitride to strengthen the interlayer connection and optimize the electronic structure. The resulting material (CN-Cu) demonstrated an enhanced support effect for Pd catalyzed Suzuki cross-coupling reactions under light illumination. Detailed characterizations showed that Cu species were atomically incorporated in intra/interlayer of CN framework through coordinating with pyridinic nitrogen, leading to improved light absorption and more efficient charge carrier transfer. More importantly, the electronic effect of CN-Cu to the surface Pd was enhanced by the electron drift from Cu to N, thereby rendered an electron-rich Pd surface. Such Pd surfaces allowed faster electron injection from Pd(0) to the LUMO of aryl halides and therefore accelerate the rate-determining step of the coupling reaction.</p

Efficacy and Safety of Tyrosine Kinase 2/Janus Kinase 1 Inhibitor Brepocitinib for Active Psoriatic Arthritis: A Phase IIb Randomized Controlled Trial.

OBJECTIVE: Brepocitinib is a tyrosine kinase 2/Janus kinase 1 inhibitor in development for treatment of several immunological diseases. Efficacy and safety of oral brepocitinib were assessed in participants with moderately-to-severely active psoriatic arthritis (PsA) for up to 52 weeks. METHODS: This placebo-controlled, dose-ranging, phase IIb study randomized participants to brepocitinib 10 mg once daily (QD), 30 mg QD, 60 mg QD, or placebo, advancing to brepocitinib 30 or 60 mg QD at week 16. The primary endpoint was American College of Rheumatology (ACR)20 response rate at week 16. Secondary endpoints included response rates of ACR50/70, 75% and 90% improvement in Psoriasis Area and Severity Index (PASI75/90), and Minimal Disease Activity (MDA) at weeks 16 and 52. Adverse events (AEs) were monitored throughout. RESULTS: Overall, 218 participants were randomized and treated. At week 16, brepocitinib 30 and 60 mg QD groups had significantly greater ACR20 response rates (66.7% [P = 0.0197] and 74.6% [P = 0.0006], respectively), versus placebo (43.3%) and significantly higher ACR50/70, PASI75/90, and MDA response rates. Response rates were maintained or improved through week 52. AEs were mostly mild/moderate; serious AEs (15) in 12 (5.5%) participants included infections in 6 (2.8%) in brepocitinib 30 and 60 mg QD groups. No major adverse cardiovascular events or deaths occurred. CONCLUSION: Brepocitinib 30 and 60 mg QD were superior to placebo at reducing signs and symptoms of PsA. Brepocitinib was generally well tolerated throughout the 52-week study with a safety profile consistent with other brepocitinib clinical trials