Synthesis of 1,2-Bis(trimethylsilyl)benzene Derivatives from 1,2-Dichlorobenzenes Using a Hybrid Metal Mg/CuCl in the Presence of LiCl in 1,3-Dimethyl-2-imidazolidinone

Abstract

A practical and safe synthesis of 1,2-bis(trimethylsilyl)benzene from 1,2-dichlorobenzene and Me3SiCl was achieved by use of a hybrid metal of Mg and CuCl in the presence of LiCl in 1,3-dimethyl-2-imidazolidinone (DMI). This method does not require a toxic HMPA, provides a high yield of the product under mild conditions, and is also applied to synthesis of substituted 1,2-bis(trimethylsilyl)benzenes and poly(trimethylsilyl)benzenes.

Iodonium Salts as Benzyne Precursors

“…[38,39,41,[80][81][82] The startingm aterials, 1,2-bis(trimethylsilyl)arenes 43 are commerciallya vailable or can be obtained by disilylationr eactions of 1,2-dichlorobenzenes in moderate yields. [83] Several other aryne precursors such as (phenyl)[3-trimethylsiyl)-2-naphthyl]-iodonium triflate 45, [84] phenyl[4-(trimethylsilyl)thien-3-yl]iodonium triflate 46, [85,86] and [1-tert-butoxycarbonyl-4-(trimethylsilyl)-1 H-pyrrole-3-yl]iodonium triflate 47 [87] have been prepared similarly from the corresponding bis(trimethylsilyl) compounds and (diacetoxyiodo)benzene in the presence of TfOH (Scheme 14). Solid state structure of [1tert-butoxycarbonyl-4-(trimethylsilyl)-1 H-pyrrole-3-yl]iodonium triflate 47 wasconfirmed by X-ray crystallography.…”

Hydrogen bonding improved atom transfer radical polymerization of methyl methacrylate with a glycerol/1,3‐dimethyl‐2‐imidazolidinone green system

“…DMI is a stable polar aprotic solvent with high dielectric permittivity ( ɛ = 37.6) and large dipole moment ( μ = 4.09D), possessing a high solvation power for both organic and inorganic compounds . The solvent of DMI containing lithium chloride is widely used in the dissolution of various celluloses, and exhibits better dissolving capacity than NMP or N , N ‐dimethylacetamide (DMAc) . DMI is generally considered to be a potential alternative for toxic, carcinogenic hexamethylphosphoramide (HMPA) which served as the medium in kinds of organic reactions .…”

“…The solvent of DMI containing lithium chloride is widely used in the dissolution of various celluloses, and exhibits better dissolving capacity than NMP or N , N ‐dimethylacetamide (DMAc) . DMI is generally considered to be a potential alternative for toxic, carcinogenic hexamethylphosphoramide (HMPA) which served as the medium in kinds of organic reactions . Other applications of DMI, such as the electrodeposition of aluminum, recycling of poly(carbonate) plastic wastes were reported as well.…”

“…45 The solvent of DMI containing lithium chloride is widely used in the dissolution of various celluloses, and exhibits better dissolving capacity than NMP or N,N-dimethylacetamide (DMAc). [46][47][48][49] DMI is generally considered to be a potential alternative for toxic, Additional Supporting Information may be found in the online version of this article. carcinogenic hexamethylphosphoramide (HMPA) which served as the medium in kinds of organic reactions.…”

Improved and Practical Synthesis of [2,4,5‐Tris(trimethylsilyl)‐ phenyl](phenyl)iodonium Triflate and Utilization as a 1,4‐Benzdiyne Synthon

“…[9] Encouraged by this discovery, we studied a facile approach to benzdiyne adducts using hypervalent iodine compounds because a hypervalent benzyne precursor, (phenyl)[2-(trimethylsilyl)phenA C H T U N G T R E N N U N G yl]-A C H T U N G T R E N N U N G iodonium triflate, [10] has the highest efficiency for benzyne generation and is easy to handle. [9] Encouraged by this discovery, we studied a facile approach to benzdiyne adducts using hypervalent iodine compounds because a hypervalent benzyne precursor, (phenyl)[2-(trimethylsilyl)phenA C H T U N G T R E N N U N G yl]-A C H T U N G T R E N N U N G iodonium triflate, [10] has the highest efficiency for benzyne generation and is easy to handle.…”