573-17-1Relevant articles and documents
A simple Hückel model-driven strategy to overcome electronic barriers to retro-Brook silylation relevant to aryne and bisaryne precursor synthesis
Neal, Edward A.,Werling,Jones, Christopher R.
supporting information, p. 1663 - 1666 (2021/02/26)
ortho-Silylaryl triflate precursors (oSATs) have been responsible for many recent advances in aryne chemistry and are most commonly accessed from the corresponding 2-bromophenol. A retro-BrookO- toC-silyl transfer is a key step in this synthesis but not all aromatic species are amenable to the transformation, with no functionalized bisbenzyneoSATs reported. Simple Hückel models are presented which show that the calculated aromaticity at the brominated position is an accurate predictor of successful retro-Brook reaction, validated synthetically by a new success and a predicted failure. From this, the synthesis of a novel difunctionalized bisaryne precursor has been tested, requiring different approaches to install the twoC-silyl groups. The first successful use of a disubstitutedo-silylaryl sulfonate bisbenzyne precursor in Diels-Alder reactions is then shown.
Preparation method of 9-hydroxyphenanthrene
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Paragraph 0045-0046; 0049-0050, (2021/08/07)
The invention discloses a preparation method of 9-hydroxyphenanthrene, the preparation method comprises the following steps: taking a phenanthrene solution as a raw material, carrying out bromination, methoxylation and demethylation reaction to obtain the 9-hydroxyphenanthrene. The preparation method has the advantages of low preparation cost, high preparation efficiency, environmental friendliness, greatly improved product yield and high quality of the prepared product, is suitable for industrial production, and can be used for large-scale industrial preparation of 9-hydroxyphenanthrene and derivatives thereof.
Chiral Ligand-Mediated Nucleophilic Aromatic Substitution of Naphthoic Acids: A Fast and Efficient Access to Axially Chiral Biaryls
Nguyen, Thi Thanh Thuy,Guyon, Hélène,Nguyen, Kim Phi Phung,Boussonnière, Anne,Mortier, Jacques,Castanet, Anne-Sophie
supporting information, p. 3829 - 3833 (2020/05/25)
A transition metal-free synthesis of enantioenriched biaryls from aryllithium species has been developed. This approach relies on atropoenantioselective nucleophilic aromatic substitution (SNAr) reaction of unprotected naphthoic acids. The ability of a diverse set of chiral ligands to mediate this transformation has been investigated. 1,2-diether ligands outperform their diamine counterparts and the best enantiocontrol was obtained with readily accessible enantiopure trans-1,2-dimethoxycyclohexane. This SNAr reaction offers an efficient and rapid access to enantioenriched binaphthalenes, phenylnaphthalene, and phenanthrylnaphthalenes (up to 94:6 er).
Regioselective arene homologation through rhenium-catalyzed deoxygenative aromatization of 7-oxabicyclo[2.2.1]hepta-2,5-dienes
Murai, Masahito,Ogita, Takuya,Takai, Kazuhiko
supporting information, p. 2332 - 2335 (2019/02/27)
Combined use of oxorhenium catalysts with triphenyl phosphite as an oxygen acceptor allowed efficient deoxygenative aromatization of oxabicyclic dienes. The reaction proceeded under neutral conditions and was compatible with various functional groups. Combining this deoxygenation with regioselective bromination and trapping of the generated aryne with furan resulted in benzannulative π-extension at the periphery of the PAHs. This enabled direct use of unfunctionalized PAHs for extension of π-conjugation. Iteration of the transformations increased the number of fused-benzene rings one at a time, which has the potential to alter the properties of PAHs by fine-tuning the degree of π-conjugation, shape, and edge topology.
Preparation method of 9-bromophenanthrene
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Paragraph 0018; 0019; 0021-0024; 0025-0028, (2017/09/19)
The invention discloses a preparation method of 9-bromophenanthrene shown as in formula (II) that is shown in the description. The preparation method is characterized by including the steps of using phenanthrene shown in formula (I) that is shown in the description as a raw material, adding KBr bromination reagent, adding bromination reagent ZnAl-BrO3-LDHs into acetic acid and water mixed solvent, reacting at 20-70 DEG C for 2-5 hours to obtain reacted liquid that is post-treated to obtain the 9-bromophenanthrene shown as in the formula (II); the mas ratio of the phenanthrene shown as in the formula (I) to the KBr and ZnAlBrO3-LDHs is 1:0.9:0.6; the preparation method has the advantages that the preparation process is convenient, the reaction conditions are mild, low environmental pollution is caused, the requirements for equipment are low, bromine utilization rate is high, and the reaction time is short.
The synthesis of polyarene-modified 5-phenyl-2,2'-bipyridines via the methodology and aza-Diels-Alder reaction
Kovalev, Igor S.,Kopchuk, Dmitry S.,Khasanov, Albert F.,Zyryanov, Grigory V.,Rusinov, Vladimir L.,Chupakhin, Oleg N.
, p. 117 - 118 (2014/04/17)
Nucleophilic substitution of hydrogen () in 6-phenyl-3-(2-pyridyl)-1,2,4- triazine under the action of lithium derivatives of polynuclear arenes followed by aza-Diels-Alder reaction with norbornadiene or morpholinocyclopentene gives the novel polyarenemodified photoluminescent 5-phenyl-2,2'-bipyridine ligands.
Dinuclear Pd(i) complexes - Solely precatalysts? Demonstration of direct reactivity of a Pd(i) dimer with an aryl iodide
Bonney, Karl J.,Proutiere, Fabien,Schoenebeck, Franziska
, p. 4434 - 4439 (2013/11/19)
This report provides experimental, computational and spectroscopic data in support of the direct reactivity of a Pd(i) dimer with an aryl iodide, resulting in Br/I halogen exchange between the complex and the aryl iodide. The reactivity could not be achieved through analogous Pd(0) conditions, demonstrating the distinct reactivities at such multiple Pd-sites. Computational studies support that the direct oxidative addition to ArI by the dinuclear metal complex is energetically feasible.
Nucleophilic substitution of hydrogen in naphthalene by chloride (Cl -) in ionic liquids
Shi, Shen Yi,Kong, Ai Guo,Zhao, Xin Hua,Ding, Han Ming,Yang, Fan,Shan, Yong Kui
experimental part, p. 147 - 150 (2012/01/03)
Nucleophilic aromatic substitution of hydrogen in non-activated aromatic ring, a very rare phenomenon in organic chemistry, is found in ionic liquids containing Cl- as anion under mild reaction conditions. The reaction may be carried out by the addition of the halogen-bonding adduct (Br 2Cl-) as nucleophile to aromatic ring carbon atom, leading to the formation of the nucleophilic substitution product.
Stereoselective bromination reactions using tridecylmethylphosphonium tribromide in a "stacked" reactor
Ma, Kefeng,Li, Shaw,Weiss, Richard G.
supporting information; experimental part, p. 4155 - 4158 (2009/06/06)
(Chemical Equation Presented) A new reagent, tridecylmethylphosphonium tribromide, and new procedures for bromination reactions of unsaturated substrates (including one that allows several substrates to be reacted in sequence) are described. The procedures exploit the diffusion of components and the densities and immiscibilities of layers, including a fluorous "spacer" layer, within a reaction vessel. The stereoselectivities achieved in the reactions are superior in some cases to those found with other brominating reagents.
A new method for the oxybromination of aromatic compounds with copper(II)bromide and potassium dichromate
Badri, Rashid,Shushizadeh, Mohammad Reza
, p. 533 - 536 (2007/10/03)
A new and mild method for oxybromination of aromatic compounds with CuBr2 and K2Cr2O7 in HOAC is reported. Copyright Taylor & Francis Inc.
