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Synthesis of Decorated Carbon Structures with Encapsulated Components by Low-Voltage Electric Discharge Treatment
Abstract: Polycondensation of complexes of chloromethanes with triphenylphosphine by the action of low-voltage electric discharges in the liquid phase gives nanosized solid products. The elemental composition involving the generation of element distribution maps (scanning electron microscopy–energy dispersive X?ray spectroscopy mapping) and the component composition (by direct evolved gas analysis–mass spectrometry) of the solid products have been studied. The elemental and component compositions of the result-ing structures vary widely depending on the chlorine content in the substrate and on the amount of triphenylphosphine taken. Thermal desorption analysis revealed abnormal behavior of HCl and benzene present in the solid products. In thermal desorption spectra, these components appear at an uncharacteristically high temperature. The observed anomaly in the behavior of HCl is due to HCl binding into a complex of the solid anion HCI-2 with triphenyl(chloromethyl)phosphonium chloride, which requires a relatively high temperature (up to 800 K) to decompose. The abnormal behavior of benzene is associated with its encapsulated state in nanostructures. The appearance of benzene begins at 650 K and continues up to temperatures above 1300?K.
Bodrikov, I. V.,Pryakhina, V. I.,Titov, D. Yu.,Titov, E. Yu.,Vorotyntsev, A. V.
p. 60 - 69
(2022/03/17)

A method for producing o-dichlorobenzene by one-pot method of o-nitrochlorobenzene as raw material
The present invention relates to a method for producing o-dichlorobenzene by a pot method of producing o-nitrochlorobenzene as raw material. Based on a continuous reactor, the continuous reactor is a reaction device connected to the reaction kettle and the catalyst packing tower, the opening of the reaction kettle is directly connected to the inlet at the bottom of the tower, the reaction kettle is provided with a feeding port and an aeration port, the catalyst packing tower top is provided with a gas inlet outlet, o-nitrochlorobenzene and continuously passed chlorine as raw material, with peroxide and azode complex catalyst as the catalyst, at 225-255 ° C, 0.11- Under the condition of 0.15Mpa, the denitrochlorination reaction was carried out in a continuous reactor to generate o-dichlorobenzene and tail gas nitrate chloride, and o-dichlorobenzene was elicitated from the top outlet of the tower along with the tail gas nitrate chloride, and the liquid o-dichlorobenzene, o-dichlorobenzene and tail gas nitroyl chloride were condensed to a residence time of 5-20min in the catalyst packing column. The high-temperature, short-term synthesis of o-dichlorobenzene, energy consumption is significantly reduced, there are few by-products, no isomers, and the conversion rate is high, up to 95%.
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Paragraph 0019-0025

(2022/01/05)

Facile Synthesis of a Fully Fused, Three-Dimensional ?-Conjugated Archimedean Cage with Magnetically Shielded Cavity
The synthesis of molecular cages consisting of fully fused, ?-conjugated rings is rare due to synthetic challenges including preorganization, large strain, and poor solubility. Herein, we report such an example in which a tris-2-aminobenzophenone precursor undergoes acid-mediated self-condensation to form a truncated tetrahedron, one of the 13 Archimedean solids. Formation of eight-membered [1,5]diazocine rings provides preorganization and releases the strain while still maintains weak ?-conjugation of the backbone. Thorough characterizations were performed by X-ray, NMR, and UV-vis analysis, assisted by theoretical calculations. The cage exhibits a rigid backbone structure with a well-defined cavity that confines a magnetically shielded environment. The solvent molecule, o-dichlorobenzene, is precisely encapsulated in the cavity at a 1:1 ratio with multiple ?···?, C-H···?, and halogen···πinteractions with the cage skeleton, implying its template effect for the cage closing reaction. Our synthetic strategy opens the opportunity to access more complex, fully fused, three-dimensional ?-conjugated cages.
Han, Yi,Jiao, Tianyu,Li, Zhengtao,Ni, Yong,Wu, Jishan,Wu, Shaofei,Zhang, Qiuyu,Zhu, Jun
supporting information
p. 14314 - 14321
(2021/09/13)

The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes
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.
Badgoti, Ranveer Singh,Dandia, Anshu,Parewa, Vijay,Rathore, Kuldeep S.,Saini, Pratibha,Sharma, Ruchi
p. 18040 - 18049
(2021/05/29)

NUCLEANT ENHANCING NUCLEATION OF A PROTEIN CRYSTAL AND PROTEIN CRYSTALLIZATION METHOD WITH THE SAME
A balanced-lattice-ledge nucleant having ledge inducing local densification of proteins and a balanced-lattice inducing self-organized crystal packing. Using this balanced-lattice-ledge nucleant enhances nucleation of protein crystals.
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(2021/05/07)

Dehydroxyalkylative halogenation of C(aryl)-C bonds of aryl alcohols
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.
Liu, Mingyang,Zhang, Zhanrong,Liu, Huizhen,Wu, Tianbin,Han, Buxing
supporting information
p. 7120 - 7123
(2020/07/14)

Amplification of Trichloroisocyanuric Acid (TCCA) Reactivity for Chlorination of Arenes and Heteroarenes via Catalytic Organic Dye Activation
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.
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)

Chiral fluorescent compound based on cyclophane alkane framework and preparation method and application of compound
The invention relates to a chiral fluorescent compound based on a cyclophane alkane framework and a preparation method and application of the compound. By using the rigid framework structure of cyclophane alkane, the chirality of the cyclophane alkane can be well kept under the excitation state, and accordingly high asymmetry factors are obtained. By changing R2 and R3 substituent groups, the luminescence section, CPL intensity and luminescence intensity can be regulated and controlled. By changing R1 substituent groups, a thermal-activation delayed fluorescence material is obtained. Phenazinemolecules based on the cyclophane alkane have a good circularly polarized luminescence characteristic and have potential application in the aspects of 3D optical display, information storage and transmission, confidential information recording, optoelectronic devices and even asymmetry photochemical synthesis.
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Paragraph 0061-0080

(2019/11/14)

Method for synthesizing dichlorobenzene
The invention provides a method for synthesizing dichlorobenzene, and the method comprises the following steps: taking trichlorobenzene as a substrate, adding dimethyl sulfoxide (DMSO), an aqueous solution of M(OH)n and a catalyst to form a mixture; stirring and heating the mixture; and contacting hydrogen with the mixture and heating for reaction to obtain the dichlorobenzene; the pH value of theaqueous solution of M(OH)n is great than 7, M is an alkali metal or alkaline earth metal, and n is a positive integer; and the catalyst is a metal catalyst or a metal supported catalyst.
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Paragraph 0061-0080

(2019/11/14)

Selective Hydrogenations and Dechlorinations in Water Mediated by Anionic Surfactant-Stabilized Pd Nanoparticles
We report a facile, inexpensive, and green method for the preparation of Pd nanoparticles in aqueous medium stabilized by anionic sulfonated surfactants sodium 1-dodecanesulfonate 1a, sodium dodecylbenzenesulfonate 1b, dioctyl sulfosuccinate sodium salt 1c, and poly(ethylene glycol) 4-nonylphenyl-3-sulfopropyl ether potassium salt 1d simply obtained by stirring aqueous solutions of Pd(OAc)2 with the commercial anionic surfactants further treated under hydrogen atmosphere for variable amounts of time. The aqueous Pd nanoparticle solutions were tested in the selective hydrogenation reactions of aryl-alcohols, -aldehydes, and -ketones, leading to complete conversion to the deoxygenated products even in the absence of strong Br?nsted acids in the reduction of aromatic aldehydes and ketones, in the controlled semihydrogenation of alkynes leading to alkenes, and in the efficient hydrodechlorination of aromatic substrates. In all cases, the micellar media were crucial for stabilizing the metal nanoparticles, dissolving substrates, steering product selectivity, and enabling recycling. What is interesting is also that a benchmark catalyst like Pd/C can often be surpassed in activity and/or selectivity in the reactions tested by simply switching to the appropriate commercially available surfactant, thereby providing an easy to use, flexible, and practical catalytic system capable of efficiently addressing a variety of synthetically significant hydrogenation reactions.
La Sorella, Giorgio,Sperni, Laura,Canton, Patrizia,Coletti, Lisa,Fabris, Fabrizio,Strukul, Giorgio,Scarso, Alessandro
supporting information
p. 7438 - 7446
(2018/05/29)

A method for preparing a chlorobenzene (by machine translation)
The invention benzene, chlorine is the raw material synthetic a chlorobenzene, metal sulfide as catalyst improves the reaction yield, the reaction temperature is 20 - 60 °C, benzene catalyst levels of 0.5% (Wt), reaction time 40 - 65min, the chlorobenzene the yield of 80%, benzene conversion reaches 90% or more. (by machine translation)
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Paragraph 0016; 0017; 0018; 0019; 0020; 0021

(2017/05/13)

Method for preparing mixed dichlorobenzene through batch method
The invention relates to a method for preparing mixed dichlorobenzene through a batch method. According to the present invention, benzene and chlorine gas are adopted as raw materials to synthesize dichlorobenzene, a metal sulfide is adopted as a catalyst to improve the reaction yield, the reaction temperature is 30-60 DEG C, the catalyst use amount is 0.5% (Wt) of benzene, the reaction time is 60-120 min, the dichlorobenzene yield achieves 93%, the m-dichlorobenzene yield is less than 1%, and the polychlorobenzene yield is less than 1%.
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Paragraph 0015; 0016; 0017; 0019

(2017/07/22)

PROCESS FOR THE PREPARATION OF ORGANIC HALIDES
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.
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Paragraph 00146

(2017/08/01)

Transition-metal-free dehalogenation of aryl halides promoted by phenanthroline/potassium tert-butoxide
Transition-metal-free dehalogenation of various aryl halides (iodides and bromides) can take place efficiently at 70–110?°C in the presence of a catalytic amount of 1, 10-phenanthroline and t-BuOK using THF or Dioxane as solvent. Control experiments indicated that radical transfer occurred between aryl radical and alkyl C[sbnd]H bond to generate alkyl radical.
Liu, Wei,Hou, Fanyi
p. 931 - 937
(2017/01/25)

Eco-compatible zeolite-catalysed continuous halogenation of aromatics
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.
Losch,Kolb,Astafan,Daou,Pinard,Pale,Louis
p. 4714 - 4724
(2016/09/04)

Dicamba preparation process
The invention belongs to the technical field of herbicide dicamba preparation and relates to a dicamba preparation process. The dicamba preparation process includes steps: taking benzene as a raw material to generate 1,2,4-trichlorobenzene through directional chlorination, catalysis, re-chlorination and rectification; hydrolyzing the 1,2,4-trichlorobenzene to generate a mixture of 2,5-dichlorophenol and 2,4-dichlorophenol, and separating and purifying to obtain 2,5-dichlorophenol; using the 2,5-dichlorophenol to prepare 3,6-dichlorosalicylic acid; subjecting the 3,6-dichlorosalicylic acid to methylation, saponification, acidification and the like to obtain dicamba. By optimization of technical steps and parameters, the whole dicamba preparation process has advantages of simplicity, low cost, high yield, high selectivity, remarkable reduction of wastewater and increase of equipment utilization rate.
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Paragraph 0051; 0052; 0053

(2017/04/03)

When benzene chlorination preparation chlorobenzene, O-dichlorobenzene santochlor and method
The invention discloses a method for preparing chlorobenzene, p-dichlorobenzene and o-dichlorobenzene in benzene chlorination, and relates to a preparation method of chemical raw materials. The method comprises the following steps: continuously introducing dry benzene and chlorine with a high activity and high p-dichlorobenzene selectivity catalyst into an outer circulation reactor, wherein the benzene and chlorine need sufficient retaining time, reacting at a set temperature to prepare p-dichlorobenzene, obtain o-dichlorobenzene at the same time and co-produce chlorobenzene, preparing dichlorobenzene by using the outer circulation reactor and taking the benzene and the chlorine as raw materials and metal sulfide as a catalyst, at the same time co-producing chlorobenzene, forming circulation of the materials through the introduced nitrogen and generated hydrogen chloride as power so as to obtain good stirring for prompting mixing, diffusion, heat conduction and mass transfer of the reactants. The method is rapid in reaction speed, high in capacity, large in ratio of p-dichlorobenzene and o-dichlorobenzene, free of polychlorobenzene byproduct, and high in flexibility and operation flexibility as the ratio of the chlorobenzene to the dichlorobenzene in a product can be adjusted according to demands.
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Paragraph 0033-0035

(2017/04/12)

O-dichlorobenzene synthesizing method
The invention relates to an o-dichlorobenzene synthesizing method. O-dichlorobenzene is formed through reaction of the materials including benzene, chlorine and a metalloporphyrin catalyst. The weight ratio of benzene, chlorine and the metalloporphyrin catalyst is 1:2.3:0.0001-0.1. The reaction temperature is 70-120 DEG C, reaction pressure is 1-4 atmospheric pressures, and reaction time is 2-7 hours. According to the method, metalloporphyrin serves as the catalyst, reaction conditions are optimized, and the characteristic that metalloporphyrin is high in catalytic activity and selectivity is used, so that o-dichlorobenzene is generated more easily through benzene and chlorine under special reaction conditions. Thus, generation of side products is reduced, the productivity of o-dichlorobenzene is remarkably improved, and raw material consumption is effectively reduced.
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Paragraph 0023

(2016/10/08)

A method for the synthesis of 2, 5 - dichlorophenol (by machine translation)
The invention relates to a 2, 5?Dichiorophenol synthetic method, which belongs to the technical field of the synthesis of the key intermediate chamber. The invention is composed of a pure chlorization generated 1, 2, 4?Trichlorobenzene and santochlor is easy to separate, thereby avoiding the difficulties caused by the separating of the high production cost and low production efficiency; because the 1, 2, 4?Trichlorobenzene and to two chiorophenoxy can be obtained respectively 2, 5?Dichiorophenol, utilization rate of raw materials is high, thereby avoiding the waste of the by-product, so that the production cost is greatly reduced. In addition, the two paradichlorbenzene through two different method to obtain 2, 5?Dichiorophenol. The synthesis technique of this invention is simple, the production cost is low, the utilization rate of raw materials is high, and the craft there are few by-products, less generation of three wastes, is more suitable for large-scale industrial production. (by machine translation)
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(2016/10/09)

PhPOCl2as a potent catalyst for chlorination reaction of phenols with PCl5
Phenols are easily converted to the corresponding aryl chlorides by using phosphorus pentachloride (PCl5) and a catalytic amount of phenylphosphonic dichloride (PhPOCl2), which is a new efficient method for synthesis of aryl chloride in good yields.
Wu, Jiang,Zhou, Junpeng,Shi, Yalei,Zhu, Jintao
supporting information
p. 1619 - 1624
(2016/10/09)

Thermodynamic Analysis of Isomerization Equilibria of Chlorotoluenes and Dichlorobenzenes in a Biphasic Reaction Systems Containing Highly Acidic Chloroaluminate Melts
Thermodynamics and kinetics of the isomerization of chlorotoluenes and dichlorobenzene to the technically desired meta-isomers have been studied in the presence of highly acidic chloroaluminate melts with alkali metal and organic imidazolium cations. Enthalpies of four isomerization processes in reacting systems of chlorotoluenes and dichlorobenzene were obtained from temperature dependencies of the corresponding equilibrium constants in the liquid phase. Experimental reaction enthalpies, enthalpies of vaporization, and absolute vapor pressures of chlorotoluenes and dichlorobenzene have been used for the validation of quantum-chemical methods to predict thermodynamic functions of the four reactions under study successfully. Values of the standard Gibbs energies of formation, standard enthalpies and entropies of formation of chlorotoluenes and dichlorobenzenes in the liquid and in the gas phase have been derived. These values allow optimization of liquid-liquid biphasic manufacturing technologies for halogen-substituted benzenes.
Verevkin, Sergey P.,Messner, Julia,Emel'Yanenko, Vladimir N.,Gantman, Mikhail G.,Schulz, Peter S.,Wasserscheid, Peter
p. 13152 - 13160
(2017/08/14)

Substd. photoisomerization arom. compd. method
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.
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Paragraph 0060

(2017/01/02)

Isomerisation of 1,4-dichlorobenzene using highly acidic alkali chloroaluminate melts
The isomerisation reaction of 1,4-dichlorobenzene leading to the thermodynamically favoured and technically desired 1,3-dichlorobenzene has been studied comparing highly acidic chloroaluminate melts with organic imidazolium and alkali metal ions. Interestingly, the inorganic melts show much higher reactivity and full recyclability if small AlCl3 losses are compensated and the reaction is carried out under slight HCl pressure. This journal is
Messner,Schulz,Taccardi,Kuhlmann, Sven,Wasserscheid
supporting information
p. 11705 - 11708
(2015/05/20)

Iron(III)-mediated photocatalytic selective substitution of aryl bromine by chlorine with high chloride utilization efficiency
An iron(III)-mediated photocatalytic method for the conversion of aryl, heteroaryl and polycyclic aromatic bromides to the corresponding chlorides with high selectivity has been achieved successfully. The mild reaction conditions and high chloride utilization efficiency promise a bright future for chlorination reactions. The Royal Society of Chemistry 2014.
Wang, Ying,Li, Lina,Ji, Hongwei,Ma, Wanhong,Chen, Chuncheng,Zhao, Jincai
supporting information
p. 2344 - 2346
(2014/03/21)

Efficient oxidative chlorination of aromatics on saturated sodium chloride solution
An efficient metal-free system using saturated aqueous sodium chloride/aqueous ammonium chloride solution as chlorine source and potassium persulfate as a cheap oxidant for the chlorination of various aromatic compounds including deactivated ones has been developed that proceeds without any acid additive in an excellent regioselective manner. The easy-to-handle aqueous solution/acetonitrile biphasic system as solvent and no need for precautionary measures make this process very practical. Copyright
Gu, Liuqun,Lu, Ting,Zhang, Mingyun,Tou, Lijuan,Zhang, Yugen
supporting information
p. 1077 - 1082
(2013/05/21)

Electrophilic chlorination of arenes with trichloroisocyanuric acid over acid zeolites
Trichloroisocyanuric acid (TCCA) reacts with arenes and its reactivity is highly affected by the acid strength of the reaction medium. Deactivated arenes are efficiently chlorinated by TCCA in solid acids. Our experimental results, along with DFT calculations show that chlorination using solid acid catalysis is feasible, thus leading to possible replacement of strong liquid acids used to promote this superelectrophilic reaction. We have tested several solid acids, showing the synergic need for acid strength and pore size for promoting the reaction.
Mendon?a, Gabriela F.,Bastos, Alexander R.,Boltz, Marilyne,Louis, Beno?t,Pale, Patrick,Esteves, Pierre M.,De Mattos, Marcio C.S.
p. 46 - 51
(2013/07/27)

Halogen exchange via a halogenation of diaryliodonium salts with cuprous halide
An efficient halogenation reaction has been developed with diaryliodonium salts and cuprous halides. Various diaryliodonium salts 1 could perform the reaction with readily available CuBr or CuCl in CH3CN at 80°C, assembling bromoarenes or chloroarenes in up to 92% yields. This provides us a method for the transformation from iodoarenes to other haloarenes.
Li, Jian,Liu, Li,Ding, Dong,Sun, Jiang-Tao
p. 541 - 548
(2014/01/06)

Cu(I)/cu(II)/TMEDA, new effective available catalyst of sandmeyer reaction
The system Cu(I)/Cu(II)/N,N,N',N'-tetramethylethylenediamine is a highly effi cient and accessible catalyst of Sandmeyer reaction. The reaction of aryldiazonium salts with chlorides, bromides cyanides, and thiocyanates of alkaline metals in the presence of this catalytic system leads to the formation of the corresponding aryl halides, nitriles, and thiocyanates in high yields.
Sigeev, A. S.,Beletskaya, I. P.,Petrovskii, P. V.,Peregudov, A. S.
p. 1055 - 1058,4
(2020/10/15)

TETRAZINE MONOMERS AND COPOLYMERS FOR USE IN ORGANIC ELECTRONIC DEVICES
Copolymers of formula (I): where each A is S, Se or C═C; each x is an integer from 1 to 4; each R1 is independently H, F, CN or a C1-C20 linear or branched aliphatic group; Ar is one or more substituted or unsubstituted aromatic units; and, n is an integer 5 or greater, can be formed into films or membranes that are useful as active layers in organic electronic device, such as PV solar cells, providing high power conversion efficiencies and good thermal stability. Such copolymers may be synthesized from monomers of formula (II): by Stille or Suzuki coupling reactions. Such monomers may be synthesized by a variation of the Pinner synthesis.
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(2012/01/15)

Synthesis and biological evaluation of 3-aryltyramines as fragments binding to BACE-1 and BACE-2
3-Aryltyramines were prepared in one single step from tyramine and various arenediazonium salts by radical arylation. Binding as well as enzyme inhibition data of the 14 compounds do not prove true interaction with BACE-1. In contrast, with BACE-2 inhibition and binding could be confirmed indicating that 3-aryltyramines are potential starting points for a drug discovery effort.
Fehler, Stefanie K.,Pratsch, Gerald,Huber, Walter,Gast, Alain,Hochstrasser, Remo,Hennig, Michael,Heinrich, Markus R.
supporting information; experimental part
p. 2189 - 2194
(2012/05/20)

Trichloroisocyanuric acid in 98% sulfuric acid: A superelectrophilic medium for chlorination of deactivated arenes
Trichloroisocyanuric acid (TCCA) reacts with arenes and its reactivity is highly affected by the acid strength of the reaction medium. Deactivated arenes are efficiently chlorinated by TCCA in H2SO4. Our results, along with DFT calculations and 13C NMR spectrometry suggest the formation of a monoprotonated TCCA superelectrophile as the reactive species that can efficiently transfer electrophilic Cl+ to even very weak nucleophiles, such as m-dinitrobenzene.
Mendo?a, Gabriela Fonseca,Senra, M?nica Rufino,Esteves, Pierre M.,De Mattos, Marcio C.S.
experimental part
p. 176 - 181
(2012/04/04)

PROCESS FOR PRODUCING p-DICHLOROBENZENE
To provide a novel process for producing p-dichlorobenzene satisfying both of high selectivity of p-dichlorobenzene and high conversion of chlorine at the same time. A process for continuously producing p-dichlorobenzene, which is a process for producing p-dichlorobenzene by a nuclear chlorination reaction of benzene and/or chlorobenzene with chlorine, in the presence of a Lewis acid catalyst and a phenothiazine analogue compound, said process comprising; employing a reactor having a first supply route for continuously supplying a mixed solution of benzene and/or chlorobenzene and a Lewis acid catalyst to a reactor, a second supply route for continuously supplying a mixed solution of benzene and/or chlorobenzene and a phenothiazine analogue compound to the above reactor, and a third supply route for continuously supplying chlorine to the above reactor; and supplying these raw materials for the reaction by opening the above first supply route and third supply route in random order at the initiation of reaction, and then opening the above second supply route.
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Page/Page column 7

(2011/08/08)

Kinetic study of the hydrogenolysis of polychlorobenzenes over a Pd/C catalyst in an alkaline aqueous-n-hexane system
The kinetics of the hydrogenolysis of chlorobenzene, dichlorobenzenes and some trichlorobenzenes over a 10% Pd/C catalyst was studied using a multiphase system. The reactions were carried out in a batch reactor with an aqueous NaOH/n-hexane solution of chloroaromatic compound as the liquid phase. Benzene was the final product of the hydrogenolysis of all the compounds studied. Hydrogenolysis was more effective in the presence of in situ generated hydrogen than gaseous hydrogen. The initial reaction rates and TOFs of dichlorobenzenes and trichlorobenzenes were slightly lower than those of chlorobenzene. The position of the chlorine atoms in trichlorobenzenes affects the kinetics of the removal of the first chlorine from these molecules. The differences in chlorine reactivity were explained by the inductive and steric effects induced by the benzene-Cl bonds.
Anusiewicz, Iwona,Janiak, Tadeusz,Okal, Janina
experimental part
p. 797 - 801
(2010/07/06)

Chlorination of aromatics with trichloroisocyanuric acid (TCICA) in bronsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf]: An economical, green protocol for the synthesis of chloroarenes
A survey study on electrophilic chlorination of aromatics with trichloroisocyanuric acid (TCICA) in Bronsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf] is reported. The reactions are performed under very mild conditions (at ～50°C) and give good to excellent yields, depending on the substrates. Chemoselectivity for mono- v. dichlorination can be tuned by changing the arene-to-TCICA ratio and the reaction time. The survey study and competitive experiments suggest that triprotonated/protosolvated TCICA is a selective/moderately reactive transfer-chlorination electrophile. Density functional theory was used as guide to obtain further insight into the nature of the chlorination electrophile and the transfer-chlorination step. CSIRO 2007.
Hubbard, Abigail,Okazaki, Takao,Laali, Kenneth K.
p. 923 - 927
(2008/03/17)

Novel catalysts for dechlorination of polychlorinated biphenyls (PCBs) and other chlorinated aromatics
Diiron complexes of fluorene and fluorene* (1,2,3,4,5,6,7,8,9- nonamethylfluorene) have been found to be catalysts for the dechlorination of chlorinated aromatics, such as PCBs. The Royal Society of Chemistry.
Fletcher, Andrew E. D.,Moss, James,Cowley, Andrew R.,O'Hare, Dermot
p. 2971 - 2973
(2008/03/11)

Natural kaolinitic clay: A remarkable catalyst for highly regioselective chlorination of arenes with Cl2 or SO2Cl2
Natural kaolinitic clay containing transition metals such as Fe and Ti in its lattice has been found to exhibit unusual regioselectivity in the liquid-phase chlorination of arenes with either Cl2 or SO 2Cl2 as the chlorinating agent para-Chlorinated products are predominant for most of the substrates with an exceptional case of ortho-selectivity for the chlorination of aniline.
Jayachandran,Phukan, Prodeep,Daniel, Thomas,Sudalai
p. 972 - 975
(2007/10/03)

Method for separating substances
An objective of the present invention is to provide electrophoretic separation methods and devices that enable the various features of a substrate surface that comes in contact with an electrophoresis medium to be controlled. The present invention provides methods for electrophoresing substances, which comprises the steps of: (a) adding a substance to be analyzed to an electrophoresis medium retained in a substrate, whose surface that has come in contact with the electrophoresis medium has been coated with a polymer membrane; and (b) adding electrophoretic pressure to the electrophoresis medium. For example, the use of a plasma-polymerized membrane allows the formation of a membrane with homogeneous quality and thickness on the surface of an arbitrary shape. In addition, desired characteristics can be conferred on the surface through selection of monomeric substances. Protein adsorption onto micro-chips can be effectively prevented as well.
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(2008/06/13)

METHOD FOR PRODUCING P-DICHLOROBENZENE
In a process for preparing p-dichlorobenzene by nuclear chlorination of benzene and/or chlorobenzene as the starting material with chlorine molecules, chlorination is carried out using aluminum chloride in an amount of 0.1 - 3 millimols per mol of the starting material and phenothiazines such as 10H-phenothiazine-10-carboxylic acid phenyl ester in an amount of 0.1 - 0.9 mols per mol of aluminum chloride so as to be a chlorination degree in a range of 1.2 - 2.5, by which p-dichlorobenzene can be obtained in a high para-selectivity and a short reaction time.
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(2008/06/13)

PROCESS FOR HALOGENATION OF BENZENE AND BENZENE DERIVATIVES
In a process of halogenation of benzene or benzene derivatives, di-substituted halobenzene derivatives having para-aromatic compounds or tri-substituted halobenzene derivatives having 1,2,4-substituted aromatic compounds are selectively produced. In halogenation of benzene or benzene derivatives, a fluorine-containing zeolite catalyst such as L-type zeolite, or a zeolite catalyst having the crystal size of at most 100 nm is used. The reaction is preferably effected in the presence of a solvent, and the solvent is preferably a halogenated compound.
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(2008/06/13)

N-halosuccinimide/BF3-H2O, efficient electrophilic halogenating systems for aromatics
N-Halosuccinimides (NXS, 1) are efficiently activated in trifluoromethanesulfonic acid and BF3-H2O, allowing the halogenations of deactivated aromatics. Because BF3-H2O is more economic, easy to prepare, nonoxidizing, and offers sufficiently high acidity (-H0 ≈ 12, only slightly lower than that of trifluoromethanesulfonic acid), an efficient new electrophilic reagent combination of NXS/BF3-H2O has been developed. DFT calculations at the B3LYP/6-311++G**//B3LYP/6-31G* level suggest that protonated N-halosuccinimides undergo further protosolvation at higher acidities to reactive superelectrophilic species capable either in the transfer of X+ from the protonated forms of NXS to the aromatic substrate or in forming a highly reactive and solvated X+ which would readily react with the aromatic substrates. Structural aspects of the BF 3-H2O complex have also been investigated.
Prakash, G. K. Surya,Mathew, Thomas,Hoole, Dushyanthi,Esteves, Pierre M.,Wang, Qi,Rasul, Golam,Olah, George A.
p. 15770 - 15776
(2007/10/03)

Formation and destruction of chlorinated pollutants during sewage sludge incineration
The limitations facing land filling and recycling and the planned ban on sea disposal of sludge leads to the expectation that the role of sludge incineration will increase in the future. The expected increase in sludge incineration will also increase scrutiny of the main drawback to sewage sludge incineration-the formation of hazardous air pollutants (HAPs). Despite the extensive body of knowledge available on sewage sludge combustion, very few studies have been conducted on the formation of HAPs during sludge combustion. In this work, the interactions between sewage sludge pyrolysis products and sludge ash were investigated using a dual chamber flow reactor system and a horizontal laboratory scale reactor. The results of this study shows that sludge ash can catalyze oxidation and chlorination of organics. In the absence of HCl in the gas stream, sludge ash acts as an oxidizing catalyst, but in the presence of HCl, sludge ash acts as a chlorination catalyst producing high yields of organochloride compounds.
Fullana, Andres,Conesa, Juan A.,Font, Rafael,Sidhu, Sukh
p. 2953 - 2958
(2007/10/03)

Concerted process for the production of an alkenyl substituted aromatic compound
An integrated process of preparing a C2-5 alkenyl-substituted aromatic compound using a C6-12 aromatic compound and a C2-5 alkane as raw materials. The process involves two reaction steps operating in tandem, the first reaction step reacts the C6-12 aromatic compound with hydrogen chloride and molecular oxygen in the presence of a catalyst to yield water and mono-, di-, tri-, and higher chlorinated aromatic adducts. The chlorinated compounds from the first reaction step are reacted with ethane in the second reaction step to produce alkane-substituted aromatic compounds which spontaneously dehydrogenate to an alkenyl-substituted aromatic compound and hydrogen chloride. After separating the alkenyl-substituted aromatic product from the hydrogen chloride, the hydrogen chloride is recycled to the first reaction step so that there is no net production or consumption of hydrogen chloride.
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(2008/06/13)

Thermolysis of hexachlorocyclohexane in a flow-through packed reactor
Thermolysis of hexachlorocyclohexane in a flow-through packed system in an inert gas atmosphere was studied.
Kut'in,Gubanova,Zorin,Zanozina,Markova,Suprunova,Bykova
p. 1518 - 1522
(2007/10/03)

Halogenation of Aromatic Compounds by N-chloro-, N-bromo-, and N-iodosuccinimide
An efficient and mild method for the halogenation of aromatic compounds using N-chloro-, N-bromo-, and N-iodosuccinimide in the presence of NH 4NO3 or FeCl3 in acetonitrile was developed.
Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Satsumabayashi, Koko,Horaguchi, Takaaki
p. 932 - 933
(2007/10/03)

Electrophilic aromatic chlorination and haloperoxidation of chloride catalyzed by polyfluorinated alcohols: A new manifestation of template catalysis
We have demonstrated that a polyfluorinated alcohol, 2,2,2-trifluoroethanol, solvent enables haloperoxidase type activity and the oxychlorination of arenes (benzene and its alkylated derivatives) without a metal catalyst. The polyfluorinated alcohol has a dual function; it catalyzes electrophilic chlorination of less reactive arenes by several orders of magnitude and oxidation of chloride at lower H+ concentrations. DFT calculations show that a complementary charge template in the transition state explains the catalysis of the electrophilic chlorination. Copyright
Ben-Daniel, Revital,De Visser, Samuel P.,Shaik, Sason,Neumann, Ronny
p. 12116 - 12117
(2007/10/03)

A new advanced method for heterogeneous catalysed dechlorination of 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes in hydrocarbon solvent
A new advanced method for dechlorination of 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes in organic solvent catalysed by palladium on carbon support and solid hydrazine hydrochloride yields benzene in short reaction times. The catalyst system can be efficiently reused for several cycles. Ultrasound radiation of the heterogeneous catalyst reaction increases remarkably the rate of dechlorination.
Rodríguez, J. Gonzalo,Lafuente, Antonio
p. 9645 - 9647
(2007/10/03)

Formation and decomposition of chloroaromatic compounds in chlorine-containing benzene/oxygen flames
Premixed chlorine-containing, fuel-rich, low-pressure benzene/oxygen flames were analysed for the formation of (oxygenated) chloroaromatic compounds and their radicals by means of the condensation/radical-scavenging method (Hausmann, M., Homann, K.-H., 1995. Ber. Busenges. Phys. Chem. 99, 853-862). Several chlorinated organic compounds (methyl chloride, t-butyl chloride, chlorobenzene, chloroform) were used as additives within a maximum concentration of 10% of total fuel. Product identification and quantification were performed by GC/MS. The extent of formation of chloroaromatic compounds in these flames was largest in the cases of chlorobenzene and chloroform as additives. For chlorobenzene, 12 different chloroaromatics could be analysed in between C7H7Cl and C12H9Cl. Their formation is mainly due to conversion of initial chlorobenzene into substituted or oxidised derivatives, or growth products. Additional chlorination of aromatics is shown to be of minor importance in chlorobenzene-containing flames. Three isomeric (o/m/p) scavenging products could be identified for the chlorophenyl radical. In the chloroform case, 15 chloroaromatics could be analysed in between C6H5Cl and C14H9Cl. The weak C-Cl bond in chloroform is responsible for the high extent of chloroaromatics formation, either by Cl abstraction from the additive or by chlorination reactions via Cl radicals. Additionally, specific pathways to (di)chloroaromatics and chlorinated fulvene-type structures are outlined via CHCl2 and CCl2 radicals.
Burfeindt,Homann
p. 439 - 447
(2007/10/03)

METHOD FOR PRODUCING AMINOCARBAZOLES
Disclosed is a method for producing an aminocarbazole by catalytically reducing a nitrocarbazole, wherein as a catalyst is used an active nickel-based catalyst prepared by contacting a nickel-based catalyst with an alkali and an iron compound under a hydrogen gas or inert gas atmosphere in an inert solvent, and according to the method of the present inventions decrease in reaction speed, decrease in yield of a product or the like depending upon the lot of the starting nitrocarbazoles can be prevented, and aminocarbazoles can be produced in a good yield constantly.
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(2008/06/13)

Dehalogenation of polychloroarenes with sodium formate in propan-2-ol catalyzed by RhCl(PPh3)3
Polychloroarenes can be dehalogenated with sodium formate in propan-2-ol using RhCl(PPh3)3 as the catalyst. The hydrogenolysis of 1,2,4-trichlorobenzene is selective to 1,2-dichlorobenzene, whereas the hydrogenolysis of 1,3- and 1,4-dichlorobenzene is sequential and selective according to the sequence: chlorobenzene > benzene.
Atienza,Esteruelas,Fernandez,Herrero,Olivan
p. 775 - 776
(2007/10/03)

Reactions of 2,4,6-trichlorophenol on model fly ash: Oxidation to CO and CO2, condensation to PCDD/F and conversion into related compounds
Thermal treatment of 2,4,6-trichlorophenol on a magnesium silicate-based model fly ash in the temperature range between 250°C and 400°C leads predominantly to carbon monoxide and carbon dioxide. The fraction of 2,4,6-trichlorophenol which is oxidized to CO and CO2 increases from 3% at 250°C to 75% at 400°C. Further products are polychlorinated benzenes, dibenzo-p-dioxins, dibenzofurans and phenols. The homologue and isomer patterns of the chlorobenzenes suggest chlorination in the ipso-position of the trichlorophenol. The formation of PCDD from 2,4,6-trichlorophenol and 2,3,4,6-tetrachlorophenol on municipal solid waste incinerator fly ashes and model fly ash were compared and the reaction order calculated.
Hell,Stieglitz,Altwicker,Addink,Will
p. 697 - 702
(2007/10/03)