24045-96-3

Upstream product

• 16188-57-1 2-iodo-4-methylphenol 
• 98-59-9 p-toluenesulfonyl chloride 

Downstream Products

• 81763-63-5 2-iodo-4-methyl-5-nitrophenyl-p-toluenesulphonate 
• 24045-97-4 C₂₈H₂₆O₆S₂ 
• 3899-96-5 4-methylphenyl tosylate 
• 81763-64-6 2-iodo-4-methyl-5-nitrophenol 
• 81763-65-7 2-iodo-4-methyl-5-nitroanisole 

Relevant academic research and scientific papers

Pd(OAc)2-catalyzed domino reactions of 1,2-dihaloarenes and 2-haloaryl arenesulfonates with Grignard reagents: efficient synthesis of substituted fluorenes

Pd(OAc)2-catalyzed domino reactions of 1,2-dihalobenzenes and 2-haloaryl arenesulfonates with hindered Grignard reagents to form substituted fluorenes, which are believed to occur through palladium associated aryne intermediates, are described. Such palladium associated aryne reaction pathway was found to be favored by omitting the use of phosphine and N-heterocyclic carbene ligands for palladium catalysts and with better leaving groups. Our study suggested that Pd(leaving group)X associated arynes should be formed first and the sp3 C-H activation preferentially occurred at benzylic C-(1°)H bonds. The work described here provides a high yield, one-step access to substituted fluorenes from readily available 1,2-dihalobenzenes and 2-haloaryl arenesulfonates and hindered Grignard reagents, and this substituted fluorene-making method may find applications in the preparation of substituted fluorene-containing molecules including polymers.

Pd(OAc)2-catalyzed Domino reactions of 1-chloro-2-haloarenes and 2-haloaryl tosylates with hindered Grignard reagents via palladium-associated arynes

(Chemical Equation Presented) The palladium-associated aryne generation strategy and Pd(OAc)2-catalyzed annulative Domino reactions of 1-chloro-2-halobenzenes and 2-haloaryl tosylates with hindered Grignard reagents via palladium-associated arynes are described. The palladium-associated aryne generation strategy described here not only allows the high yield, one-step access to potentially useful substituted fluorenes from readily available 1-chloro-2-halobenzenes and 2-haloaryl tosylates, but may also lead to the development of other tandem reactions based on these readily available ortho leaving group bearing haloarenes.

Novel Homologation Reaction of Arylzincates Bearing a Leaving Group at the Ortho and Meta Positions

Arylzincates bearing a leaving group at the ortho, meta, and para positions were generated by iodine/zinc exchange reaction of the corresponding iodoaryl sulfonates with Bu3ZnLi, and their reactivity was investigated via product analysis after hydrolysis and treatment with iodine. Zincates derived from o-iodophenyl triflates and tosylate underwent homologation reaction to give o-butylphenylzinc species. o-Benzyne as an intermediate of the reaction was demonstrated by the lack of regioselectivity for trisubstituted zincates. Zincates derived from m-iodophenyl triflates also underwent homologation leading to m-butylphenylzinc species. Similar product ratios observed in the reactions of regioisomeric trisubstituted iodophenyl triflates as well as the formation of radical reaction byproducts suggested the involvement of m-benzyne intermediate. p-(Trifluoromethane-sulfonyloxy)phenylzincate was thermally stable at room temperature; generation of p-benzyne was not observed.

13C Chemical Shifts of Symmetrically Substituted Biphenyls: Unambiguous Signal Assignment for the Carbons ortho and para to an Aryl Group

The natural abundance 13C NMR spectra of 2,2'-dimethyl-, 2,2'-dimethoxy- and 2,2'-dihydroxybiphenyls, and a series of 2,2'-dimethoxy-5,5'-disubstituted biphenyls were recorded.Unambiguous signal assignments of the carbons ortho and para to an aryl ring in