694-80-4Relevant academic research and scientific papers
Direct bromodeboronation of arylboronic acids with CuBr2 in water
Tang, Yan-Ling,Xia, Xian-Song,Gao, Jin-Chun,Li, Min-Xin,Mao, Ze-Wei
supporting information, (2021/01/05)
An efficient and practical method has been developed for the preparation of aryl bromides via the direct bromodeboronation of arylboronic acids with CuBr2 in water. This strategy provides several advantages, such as being ligand-free, base-free, high yielding, and functional group tolerant.
The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes
Badgoti, Ranveer Singh,Dandia, Anshu,Parewa, Vijay,Rathore, Kuldeep S.,Saini, Pratibha,Sharma, Ruchi
, p. 18040 - 18049 (2021/05/29)
An efficient, metal-free, and sustainable strategy has been described for the ipso-functionalization of phenylboronic acids using air as an oxidant in an aqueous medium. A range of carbon materials has been tested as carbocatalysts. To our surprise, graphite was found to be the best catalyst in terms of the turnover frequency. A broad range of valuable substituted aromatic compounds, i.e., phenols, anilines, nitroarenes, and haloarenes, has been prepared via the functionalization of the C-B bond into C-N, C-O, and many other C-X bonds. The vital role of the aromatic π-conjugation system of graphite in this protocol has been established and was observed via numerous analytic techniques. The heterogeneous nature of graphite facilitates the high recyclability of the carbocatalyst. This effective and easy system provides a multipurpose approach for the production of valuable substituted aromatic compounds without using any metals, ligands, bases, or harsh oxidants.
Metal- and base-free synthesis of aryl bromides from arylhydrazines
Phuc Tran, Dat,Nomoto, Akihiro,Mita, Soichiro,Dong, Chun-ping,Kodama, Shintaro,Mizuno, Takumi,Ogawa, Akiya
supporting information, (2020/05/08)
An efficient method was developed to synthesize brominated aromatic compounds from arylhydrazine hydrochlorides by using BBr3 in DMSO/CPME (cyclopentyl methyl ether) under air at 80 °C for 1 h without the use of bases or metal catalysts. In particular, this method could be carried out satisfactorily using electron-withdrawing groups to afford aryl bromides in a moderate to excellent yields.
Dehydroxyalkylative halogenation of C(aryl)-C bonds of aryl alcohols
Liu, Mingyang,Zhang, Zhanrong,Liu, Huizhen,Wu, Tianbin,Han, Buxing
supporting information, p. 7120 - 7123 (2020/07/14)
We herein report Cu mediated side-directed dehydroxyalkylative halogenation of aryl alcohols. C(aryl)-C bonds of aryl alcohols were effectively cleaved, affording the corresponding aryl chlorides, bromides and iodides in excellent yields. Aryl alcohols could serve as both aromatic electrophilic and radical synthetic equivalents during the reaction.
Amplification of Trichloroisocyanuric Acid (TCCA) Reactivity for Chlorination of Arenes and Heteroarenes via Catalytic Organic Dye Activation
Rogers, David A.,Bensalah, Adam T.,Espinosa, Alvaro Tomas,Hoerr, John L.,Refai, Fares H.,Pitzel, Amy K.,Alvarado, Juan J.,Lamar, Angus A.
supporting information, p. 4229 - 4233 (2019/06/17)
Heteroarenes and arenes that contain electron-withdrawing groups are chlorinated in good to excellent yields (scalable to gram scale) using trichloroisocyanuric acid (TCCA) and catalytic Brilliant Green (BG). Visible-light activation of BG serves to amplify the electrophilic nature of TCCA, providing a mild alternative approach to acid-promoted chlorination of deactivated (hetero)aromatic substrates. The utility of the TCCA/BG system is demonstrated through comparison to other chlorinating reagents and by the chlorination of pharmaceuticals including caffeine, lidocaine, and phenazone.
PROCESS FOR THE PREPARATION OF ORGANIC BROMIDES
-
Paragraph 00139; 00143, (2017/07/28)
The present invention provides a process for the preparation of organic bromides, by a radical bromodecarboxylation of carboxylic acids with a bromoisocyanurate.
PROCESS FOR THE PREPARATION OF ORGANIC HALIDES
-
Paragraph 00143, (2017/08/01)
The present invention provides a halo-de-carboxylation process for the preparation of organic chlorides, organic bromides and mixtures thereof, from their corresponding carboxylic acids, using a chlorinating agent selected from trichloroisocyanuric acid (TCCA), dichloroisocyanuric acid (DCCA), or combination thereof, and a brominating agent.
A paradichlorbenzene dichloroethane pharmaceutical intermediates method for synthesis of O-chloro-bromobenzene (by machine translation)
-
Paragraph 0018; 0019; 0020, (2016/11/17)
A paradichlorbenzene dichloroethane pharmaceutical intermediates method for synthesis of O-chloro-bromobenzene, comprising the following steps : (i) in the reaction container by adding O-aminochlorobenzene 0.8mol, aqueous solution 100 ml, control the stirring speed in the 300-500rpm, sodium bromide solution to 300 ml, control the temperature of the solution for 6-9°C, potassium sulfite dropping 0.8mol soluble in 100-120ml in aqueous solution, keeping the temperature of the solution after the adding the 35-40°C, potassium iodide test for determining the end point of the reaction, the diazonium salt is generated (3); the stannous chloride (ii) 0.12mol, the mass fraction is 50-70% sodium bromide solution of 200-300ml mixed in the reaction vessel, heating the solution temperature to 90-92°C, dropping step (i) generating the diazotizing solution, after adding water vapor distillation, separating the organic layer, the aqueous layer is extracted with a solvent a certain number of times, the merger with the extracted oil, used for quality score for sequentially 30-40% phosphoric acid washing, and washing solution, salt solution washing, dehydrating agent dehydration, vacuum distillation to extracting distilled, collecting 180-185 °C fraction, O-chloro-bromobenzene may be colorless transparent product. (by machine translation)
Eco-compatible zeolite-catalysed continuous halogenation of aromatics
Losch,Kolb,Astafan,Daou,Pinard,Pale,Louis
, p. 4714 - 4724 (2016/09/04)
A completely eco-compatible halogenation reaction of arenes has been developed allowing high conversions (>95%) of iodobenzene with nearly 100 kg iodobenzene converted per kgcat in one day. Several solid acids, zeolites being the most promising, have been successfully tested in the chlorination reaction of iodobenzene by using trichloroisocyanuric acid (TCCA), a green chlorination agent. H-?BEA zeolites were found to be the most active catalysts for this model halogenation reaction. A strong structure-activity relationship could be established by thorough characterisation (SEM, BET, XRD, FTIR) of various synthetic zeolites. Indeed, nano-sized ?BEA zeolites and more specifically nanosponge-like ?BEA crystals exhibited the highest catalytic performance with a conversion up to 100% and a selectivity toward monochlorinated products up to 98%. Finally, the gained knowledge was applied to set-up an eco-compatible continuous flow halogenation process of different aromatics catalysed by H-?BEA zeolites.
Substd. photoisomerization arom. compd. method
-
Paragraph 0066, (2017/01/02)
Isomerizing substituted aromatic compounds (I), comprises carrying out isomerization in the presence of a salt melt, which contains a metal compound (II) and at least one metal compound (III). Isomerizing substituted aromatic compounds of formula (Ar1-R n) (I) or their mixtures, comprises carrying out isomerization in the presence of a salt melt, which contains a metal compound of formula ([M1][X1] m 1) (II) and at least one metal compound of formula ([M2][X2] m 2) (III). Ar1 : n-valent aryl radical; R : halo, alkyl, fluoroalkyl, aryl, alkyl-aryl or amino; M1 : Al, Ga, In, Cu, Fe, Co or Ni; X1, X2 : halo, preferably Cl or Br; M2, m2 : alkaline earth metal or alkali metal, where M2 is preferably Li, Na, or K; m1 : Al, Ga, In, Fe(III), Co, Ni or Cu(II); and n : >= 2, preferably 2.
