315-50-4

Upstream product

• 4523-45-9 1-amino-4-methylnaphthalene 
• 573-03-5 4-fluoro-1-naphthoic acid 
• 90-12-0 1-Methylnaphthalene 
• 823-96-1 Trimethylboroxine 
• 341-92-4 1-fluoro-4-nitronaphthalene 

Downstream Products

• 571-58-4 1,4-dimethylnaphthalene 
• 23668-55-5 trans-1-<4-Fluor-1-methyl-naphthyl-(2)>-2-(o-iodphenyl)-aethylen 

Relevant academic research and scientific papers

A methylation platform of unconventional inert aryl electrophiles: Trimethylboroxine as a universal methylating reagent

Methylation is one of the most fundamental conversions in medicinal and material chemistry. Extension of substrate types from aromatic halides to other unconventional aromatic electrophiles is a highly important yet challenging task in catalytic methylation. Disclosed herein is a series of transition metal-catalyzed methylations of unconventional inert aryl electrophiles using trimethylboroxine (TMB) as the methylating reagent. This transformation features a broad substrate type, including nitroarenes, benzoic amides, benzoic esters, aryl cyanides, phenol ethers, aryl pivalates and aryl fluorides. Another important merit of this work is that these widespread "inert"functionalities are capable of serving as directing or activating groups for selective functionalization of aromatic rings before methylation, which greatly expands the connotation of methylation chemistry.

Fluorination of Bi- and polycyclic aromatic hydrocarbons with N-fluorobis(phenylsulfonyl)amine in the absence of solvent

Reactions of N-fluorobis(phenylsulfonyl)amine with naphthalene, 1-methylnaphthalene, phenanthrene, anthracene, and pyrene without solvent were investigated. Sometimes the fluorination of aromatic compounds with N-fluorobis(phenylsulfonyl)amine without solvent proceeded more selectively than at the use of fluorinating reagents in solution.

First application of ionic liquids in electrophilic fluorination of arenes; Selectfluor (F-TEDA-BF4) for "green" fluorination

The NF fluorinating agent F-TEDA-BF4 dication salt (Selectfluor) 1 dissolves in imidazolium-based ionic liquids [emim][OTf] 7, [emim][BF4] 8, [bmim][PF6] 9 and [bmim][BF4] 10 (assisted by sonication), providing a convenient medium for fluorination of arenes under essentially acid-free conditions in a simple set-up (no volatile solvent; simple extraction of the aromatics without aqueous work-up), from which the ionic liquid can be easily recycled and reused. Comparative studies in [emim][OTf] 7 with anisole as substrate show that 1 is superior to NFTh-BF4 (Accufluor) 2 and that the N-fluoropyridinium salt NFPy-B2F7 4 is least effective. The scope of the reaction has been surveyed. Substrate selectivity (k mesitylene: k durene = 10) measured in competitive experiments in 7 is clearly indicative of a conventional polar mechanism. Substrate selectivity measured without the ionic liquid in MeCN solvent is also indicative of a polar mechanism but exhibits lower magnitude (k mesitylene: kdurene = 6). Addition of dicyclohexano-24-crown-8 to the fluorination reaction mixture (1 and anisole) in 7 reduced the conversion but did not change the isomer distribution. AM1 minimization was used to model the complexation of 1 with this crown. With reactive aromatics optimal fluorination yields in ionic liquids (using 1 equivalent of the NF reagent) are around 50% (higher for naphthalene). A key control experiment suggests that the free base (produced upon transfer-fluorination) could complex to unreacted 1 (generating a bulky dimer complex which may be ineffective for fluorine transfer) in competition to N-protonation.

Selective and efficient direct fluorination of polycyclic aromatic hydrocarbons using 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)

A new N-F fluorinating reagent 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Accufluor NFTh) was effectively used for selective fluorination of polycyclic aromatics. Naphthalene was site-selectively fluorinated to 1-fluoronaphthalene, phenanthrene to 9-fluorophenanthrene, and pyrene to 1-fluoropyrene. In a series of substituted naphthalenes the regioselectivity and effectiveness of fluorination depended on the position and the nature of the substituents.