1577232-65-5

Upstream product

• 1344089-60-6 N,N-bis(3-bromoprop-2-yn-1-yl)-4-methylbenzenesulfonamide 
• 536-74-3 phenylacetylene 
• 19821-84-2 1-bromohept-1-yne 
• 18773-54-1 4-methyl-N,N-diprop-2-ynylbenzenesulfonamide 
• 932-87-6 1-Bromo-2-phenylacetylene 

Downstream Products

• 1577232-53-1 7-bromo-5-phenyl-4-(phenylethynyl)-2-tosylisoindoline 

Relevant academic research and scientific papers

Synthesis of phenolic compounds by trapping arynes with a hydroxy surrogate

Trapping of arynes with various nucleophiles provides a range of heteroatom-functionalized arene derivatives, but the corresponding reaction with water does not provide phenol derivatives. Silver trifluroacetate (AgO2CCF3) can nicely solve this problem. It was found that in typical organic solvent, AgO2CCF3 readily reacts with arynes to generate trifluoroacetoxy organosilver arene intermediate, which, upon treating with silica gel, provides phenolic products. This protocol can be extended to the synthesis of α-halofunctionalized phenol derivatives by simply adding NBS (N-bromosuccinimides) or NIS (N-iodosuccinimides) to the reaction along with silver trifluroacetate, which provided α-bromo or α-iodophenol derivatives in good yield. However, the similar reactions with NCS (N-chlorosuccinimides) afforded only the protonated product instead of the expected α-chlorophenols derivatives. Interestingly, substrates containing silyl substituents on 1,3-diynes resulted in α-halotrifluoroacetates rather than their hydrolyzed product. Additionally, trapping the same arynes with other oxygen-based nucleophiles containing silver counter cation, along with NXS (N-halosuccinimides), generated α-halooxyfunctionalized products.

Diaryl thioether derivatives, and preparation method thereof

The invention belongs to the field of organic synthesis, and especially relates to diaryl thioether derivatives, and a preparation method thereof. Compared with common thioether derivatives, thediaryl thioether derivatives possess following characteristics: the diaryl thioether derivatives are polycyclic compounds; the structure is more complex and diverse; and application prospect is more promising. The preparation method comprises following steps: in a water-free oxygen-free system, a diyne compound, a hydrocarbyl alkyne bromide, anhydrous acetonitrile, a transition-metal catalyst, and an organic base are mixed and reacted so as to obtain an intermediate; at 90 to 115 DEG C, the intermediate, an aryl disulfide, and methylbenzene are mixed and reacted. According to the preparation method, substrate synthesis is simple; the reagents are relatively cheap; the target molecules are obtained with high atom economy; the preparation method is green, and is friendly to the environment; and a valuable approach is provided for industrialized production of the diaryl thioether derivatives.

Hydrohalogenative aromatization of multiynes promoted by ruthenium alkylidene complexes

A new functionalization method of arynes promoted by a novel catalytic role of the Grubbs-type ruthenium alkylidene complex is described. Through a sequence of aryne formation followed by their halo-functionalization, various bis-1,3-diynes were directly converted to functionalized aryl chlorides, bromides and iodides in good yields in the presence of a catalytic amount of a ruthenium alkylidene complex and halogenated hydrocarbons such as CH2Cl2, CHCl3, CH2Br2, and CH2I2. The utility of this novel transformation is demonstrated by a formal synthesis of herbindole B.

Diels-Alder reactions of arynes in situ generated from da reaction between bis-1,3-diynes and alkynes

Diels-Alder reactions based on arynes generated directly from bis-1,3-diynes have been developed. These reactions displayed good functional group compatibility and gave moderate to high yields under mild conditions. Such synthetic methodology can be effectively used for the synthesis of complicated ring compounds.