cas 95-49-8, 2-Chlorotoluene | Articles data

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McMaster,Carol
p. 218
(1931)
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Deep compositional understanding of TBA: AlCl3 ionic liquid for its applications
Chloroaluminate ionic liquids (ILs) have been immensely used as homogeneous catalyst in Friedel-Crafts reaction. We have recently synthesized chloroaluminate ILs by reacting aluminium chloride with a hydrophobic neutral ligand i.e. tributylamine (TBA:AlCl3). The current study elaborates on the investigations of the composition of the ionic liquids at various stages of their formation. The ionic liquids were synthesized using various mole ratios of tributyl amine and aluminium chloride in range of 1:1 to 1:2.3, in presence of an aromatic solvent in a one pot reaction. Various characterization techniques like Mass spectrometry, 27Al Nuclear Magnetic Resonance, 31P Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopy were used to elucidate the formation of various moieties of the TBA:AlCl3 Ionic Liquid. This study also elaborates on the investigations of the cationic and anionic moieties and their structure-property relationship for various applications. Various Friedel-Crafts reaction of industrial importance were performed using the ionic liquid having (Al2Cl7)?moiety to assess its performance and compared with conventional processes. The synthesized products were characterised by sophisticated analytical techniques like 1H NMR, 13C NMR, FTIR, GC–MS, GC-FID, to name a few. This class of ionic liquids also have importance in various electrochemical applications like aluminium deposition and aluminium batteries.
Bhakthavatsalam, Vishnupriya,Chandra, Sudeshna,Choudhury, Rudra Prosad,Lande, Sharad V.,Pradhan, Jeevan,Sakhalkar, Mangesh
(2020/07/31)

Rate enhancements due to ultrasound in isoquinolinium dichromate and isoquinolinium chlorochromate catalyzed chlorination of aromatic compounds in presence of KHSO4/KCl
Chlorination of aromatic compounds underwent magnificent rate accelerations in isoquinolinium dichromate and isoquinolinium chlorochromate catalyzed chlorination of aromatic hydrocarbons in the presence of KCl and KHSO4. Reaction times reduced highly significantly from 4-5 h in conventional protocol to 30-40 min under sonication, followed by high yields of monochloro derivatives as products with high regioselectivity.
Rajanna,Rao, A. Sambashiva,Chakravarthi,Reddy, K. Rajendar
p. 167 - 170
(2017/12/26)

Method for producing parachlorotoluene through continuous chlorination of methylbenzene
The invention discloses a method for producing parachlorotoluene through continuous chlorination of methylbenzene. The method comprises the following steps: with an active molecular sieve as a catalyst, performing continuous chlorination on methylbenzene in a static bed, wherein a ratio of parachlorotoluene to o-chlorotoluene in the chlorination products is 1.2-6.0; performing aeration and distillation separation on the chlorination product to obtain high-purity parachlorotoluene, and enabling the separated methylbenzene and raw material methylbenzene to enter the static bed together so as toperform continuous chlorination; periodically reproducing the catalyst in the static bed; and alternately using and activating two groups or more than two groups of static beds. According to the method disclosed by the invention, continuous chlorination production of methylbenzene is realized, the ratio of parachlorotoluene to o-chlorotoluene is 1.2-6.0, the catalyst can be repeatedly used, the production cost is reduced, and solid waste emission is reduced.
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Paragraph 0016; 0018; 0020

(2018/09/28)

A process for preparing O-toluene
The present invention provides a process for preparing dichloro toluene, relates to the field of preparation of organic intermediates. The invention relates to 2, 3 - dichloro toluene, 2, 4 - dichloro toluene and 2, 5 - dichloro toluene in more than one type of raw materials, supported palladium as the catalyst, a fixed bed continuous reaction preparation of O-toluene. This invention uses the industrial by-product 2, 3 - dichloro toluene, 2, 4 - dichloro toluene and 2, 5 - dichloro toluene as the raw materials, supported palladium catalyst good selectivity, long-time use, O-chlorotoluene high yield.
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Paragraph 0015-0018

(2018/10/11)

2 - Chloro -3 - methyl benzoic acid and intermediate preparation method (by machine translation)
The invention discloses a 2 - chloro - 3 - methyl benzoic acid and intermediate preparation method. A 2 - chloro - 3 - methyl benzoic acid and intermediate preparation method, comprising the following steps, in the oxygen pressure is 0.1 mpa - 0.8 mpa under the condition of, under the action of the catalyst and promoter, the 2, 6 - dimethyl chlorobenzene to carry out oxidation reaction, can be; wherein said 2, 6 - dimethyl chlorobenzene and the oxygen molar amount ratio of 1: 1.8 - 1: 2.2. The 2 - chloro - 3 - methyl benzoic acid, in order to industrially easily available raw materials for the reaction, after treatment is simple, high yield, purity is good, small pollution to the environment, is more suitable for industrial. (by machine translation)
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Paragraph 0101; 0102

(2018/10/11)

Preparation method of aryl diazonium chlorocuprate
The invention provides a preparation method of aryl diazonium chlorocuprate. Stable salt is formed by aryl diazonium salt and chlorocuprate radicals, the aryl diazonium chlorocuprate is prepared in situ, and a complex is prepared and decomposed by controlling reaction temperature. According to the method, the diazonium salt is prepared by non-aqueous solvents, the aryl diazonium chlorocuprate is then prepared in situ, finally, Sandmeyer is performed by the aid of the difference of stability of the diazonium salt, and recovery and emission reduction functions can be achieved in practical production.
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Paragraph 0034-0038; 0042-0044

(2018/05/01)

A method of preparing O-toluene
The invention relates to a preparation method of o-chlorotoluene. Particularly, methylbenzene is used as a raw material, Cl2 is used as a chlorine source, and [BMIM]Cl-nZnCl2(n is equal to 1, 2, 2.5, and n is a molar ratio of ZnCl2 to [BMIM]Cl) acidic ionic liquid is used as a catalyst to catalyze the methylbenzene to prepare the o-chlorotoluene; the [BMIM]Cl-nZnCl2(n is equal to 1, 2 or 2.5) acidic ionic liquid is used as a chlorinated catalyst, and the Cl2 is used as the chlorine source to perform selective chlorination on the methylbenzene. According to the method, the selectivity of the o-chlorotoluene in the product can be improved, the [BMIM]Cl-nZnCl2 ionic liquid catalyst separated from the product can also be repeatedly used, so the production cost is reduced, and the method is an important method for contributing to industrial production of the o-chlorotoluene.
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Paragraph 0027-0034

(2017/08/31)

A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids leading to chlorinated arenes
A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids with inexpensive N-chlorosuccinimide (NCS) was achieved in MeCN in the presence of 10 mol% of l-proline-functionalized MCM-41-immobilized copper(i) complex [MCM-41-l-proline-CuCl] under mild conditions, yielding a variety of aryl chlorides in excellent yields. This method proved to be tolerant of a broad range of functional groups and particularly useful for the conversion of electron-deficient arylboronic acids to aryl chlorides, a transformation that is inefficient without copper catalysis. This heterogeneous copper catalyst can be recovered by a simple filtration of the reaction solution and recycled for at least 10 times without any decreases in activity.
He, Wen,Zhang, Rongli,Cai, Mingzhong
p. 764 - 770
(2017/01/13)

Mild Aliphatic and Benzylic Hydrocarbon C-H Bond Chlorination Using Trichloroisocyanuric Acid
We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr4 reduced the reaction times considerably due to the formation of chain-carrying ·CBr3 radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.
Combe, Sascha H.,Hosseini, Abolfazl,Parra, Alejandro,Schreiner, Peter R.
p. 2407 - 2413
(2017/03/11)

Visible Light-Induced Oxidative Chlorination of Alkyl sp3 C-H Bonds with NaCl/Oxone at Room Temperature
A visible light-induced monochlorination of cyclohexane with sodium chloride (5:1) has been successfully accomplished to afford chlorocyclohexane in excellent yield by using Oxone as the oxidant in H2O/CF3CH2OH at room temperature. Other secondary and primary alkyl sp3 C-H bonds of cycloalkanes and functional branch/linear alkanes can also be chlorinated, respectively, under similar conditions. The selection of a suitable organic solvent is crucial in these efficient radical chlorinations of alkanes in two-phase solutions. It is studied further by the achievement of high chemoselectivity in the chlorination of the benzyl sp3 C-H bond or the aryl sp2 C-H bond of toluene.
Zhao, Mengdi,Lu, Wenjun
supporting information
p. 4560 - 4563
(2017/09/11)

Method for preparing o-chlorotoluene through methylbenzene loop chlorination
The invention discloses a method for preparing o-chlorotoluene through methylbenzene loop chlorination. The method particularly includes the steps that iron powder or ferric trichloride is added into methylbenzene to serve as catalysts, [BMTM]Cl-nZnCl2 ionic liquid serves as an assistant (n is equal to 1, 2 or 2.5), and stirring is carried out; dry chlorine is led in, a suitable temperature is controlled under the dark condition to conduct chlorination, the o-chlorotoluene is obtained in a high-selectivity manner, and alkali liquor absorption is carried out after tail gas condensation to remove excessive unreacted chlorine; and after reacting is ended, a reacting product and the ionic liquid assistant are separated, the separated ionic liquid can be repeatedly used. Compared with the prior art, the method can well improve the methylbenzene conversion rate, and the o-chlorotoluene selectivity reaches 88%; in addition, the separated and recycled [BMTM]Cl-nZnCl2 ionic liquid is repeatedly used, the production cost is reduced, and the method is suitable for o-chlorotoluene industrial production.
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Paragraph 0024; 0026-0027

(2017/08/15)

Zinc chloride load HY molecular sieve catalytic toluene synthesis of O-toluene
The invention relates to the technical field of preparation of o-chlorotoluene, in particular to a method for synthesizing the o-chlorotoluene by catalyzing toluene through a zinc chloride load HY molecular sieve, and belongs to the technical field of toluene orientation chlorination. According to the method, the zinc chloride load HY molecular sieve is adopted as a catalyst, Cl2 is adopted as a chlorinating agent, and a liquid phase chlorination method is adopted for carrying out selective chlorination on the toluene. According to the method for preparing the o-chlorotoluene by carrying out selective chlorination on the toluene, the reaction condition is mild and easy to control, the synthetic process is simple, the adopted ZnCl2/HY catalyst is good in catalytic activity and can be separated from a product easily, pollution to the environment is small, corrosivity to equipment is small, and the method has high industrial application value.
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Paragraph 0022; 0023; 0024; 0025; 0026; 0027; 0028-0050

(2017/08/25)

Room temperature C(sp2)-H oxidative chlorination: Via photoredox catalysis
Photoredox catalysis has been developed to achieve oxidative C-H chlorination of aromatic compounds using NaCl as the chlorine source and Na2S2O8 as the oxidant. The reactions occur at room temperature and exhibit exclusive selectivity for C(sp2)-H bonds over C(sp3)-H bonds. The method has been used for the chlorination of a diverse set of substrates, including the expedited synthesis of key intermediates to bioactive compounds and a drug.
Zhang, Lei,Hu, Xile
p. 7009 - 7013
(2017/10/05)

METHOD FOR MANUFACTURING O-CHLOROTOLUENE AND P-CHLOROTOLUENE
The present invention relates to a method for manufacturing o-chlorotoluene and p-chlorotoluene. The method comprises the following steps: a) injecting chlorine gas to a reaction solution including excess toluene and producing chlorotoluene through a reaction of the toluene and the chlorine gas; and b) performing cooling after the step a). The step a) and the step b) are repeatedly performed in order. The amount of the chlorine gas injected in the step a) is the amount that the temperature of the reaction solution after the reaction in the step a) is completed is more than or equal to 50anddeg;C and less than or equal to 90anddeg;C.COPYRIGHT KIPO 2017
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Paragraph 0067-0071

(2017/09/29)

A toluene selective chlorination of synthesis of O-toluene
The invention relates to the technical field of preparation of o-chlorotoluene, in particular to a method for synthesizing o-chlorotoluene through methylbenzene selective chlorinating. The method specifically includes the step of catalyzing methylbenzene selective chlorinating to prepare o-chlorotoluene with methylbenzene as the raw material, Cl2 as the chlorinating agent and [Et3NH]Cl-nCuCl ion liquid as the catalyst, wherein n is equal to 1 or 2 or 3 and is the mole ratio of CuCl to [Et3NH]Cl. By means of the method, the selectivity of o-chlorotoluene in methylbenzene chlorinating can be improved, the [Et3NH]Cl-nCuCl ion liquid separated from a product can be repeatedly used, the reaction cost is effectively reduced, and the method is an important method beneficial to the industrial production of o-chlorotoluene.
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Paragraph 0029-0030; 0037; 0042; 0047

(2017/08/25)

Method for preparing o-chlorotoluene and p-chlorotoluene
The present invention relates to a method for preparing O-chlorotoluene and P-chlorotoluene. The method according to the present invention comprises a step of isolating and collecting non-reacted toluene from a reaction product of toluene and chlorine, and a step of removing a catalyst from the remaining reaction product by contacting the reaction product with an alkaline solution, thereby fundamentally blocking contact between the non-reacted toluene and the alkaline solution and minimizing the moisture content of the collected non-reacted toluene.COPYRIGHT KIPO 2017
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Paragraph 0085; 0086; 0088

(2017/11/14)

METHOD FOR PREPARING o-CHLOROTOLUENE AND p-CHLOROTOLUENE
The present invention relates to a method for preparing o-chlorotoluene and p-chlorotoluene. The preparation method according to the present invention is characterized in that toluene and chlorine are reacted in the presence of a certain ratio of a main catalyst and a cocatalyst, so the reaction selectivity is improved and the amount of by-products can be minimized.COPYRIGHT KIPO 2018
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Paragraph 0073-0077

(2018/04/20)

Method for preparing O-chlorotoluene
The invention discloses a method for preparing o-chlorotoluene. The method comprises the following steps: adding a raw material toluene and a FeCl3-loaded macroporous metal silica gel catalyst into a reaction kettle; introducing chlorine into the reaction kettle for a liquid-phase ring chlorination reaction between the toluene and chlorine; after the reaction is complete, aerating to remove residual chlorine and hydrogen chloride gas in the reaction liquid; rectifying the reaction liquid to separate out unreacted toluene and a little dichlorotoluene to obtain mixed chlorotoluene; and then, separating high-purity p-chlorotoluene from the mixed chlorotoluene by using a melt crystallization process. According to the method disclosed by the invention, the FeCl3-loaded macroporous metal silica gel catalyst is adopted for catalyzing the selective chlorination of toluene, the reaction is fast, the catalytic activity is high, the o-chlorotoluene selectivity is good, the requirements for the technological conditions are low, the catalyst consumption is low, the catalyst has high activity and can be recycled, and the method has a good industrial prospect.
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Paragraph 0015; 0016

(2016/10/08)

Method for preparing parachlorotoluene
The invention provides a method for preparing parachlorotoluene. The method comprises the following steps of adding raw materials of methylbenzene and catalysts into a reaction kettle, and feeding chlorine into the reaction kettle to subject methylbenzene and chlorine to a liquid phase ring chlorination reaction; performing aeration after the reaction is completed, removing chlorine and hydrogen chloride remaining in reaction liquid, and rectifying the reaction liquid to separate out un-reacted methylbenzene and a small quantity of dichlorotoluene to obtain mixed chlorotoluene; separating mixed chlorotoluene through a melt crystallization method to obtain high-purity parachlorotoluene. According to the method, AlCl3 loaded L-shaped molecular sieve based catalysts are used for catalyzing methylbenzene for selective chlorination, the reaction rate is high, the catalytic activity is high, selectivity of parachlorotoluene is good, the requirement for process conditions is low, and the catalyst use amount is small; the catalyst is high in activity and capable of being recycled, and a good industrial prospect is achieved.
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Paragraph 0018-0019

(2017/02/09)

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)

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)

Direct C(sp3)-H Cross Coupling Enabled by Catalytic Generation of Chlorine Radicals
Here we report the development of a C(sp3)-H cross-coupling platform enabled by the catalytic generation of chlorine radicals by nickel and photoredox catalysis. Aryl chlorides serve as both cross-coupling partners and the chlorine radical source for the α-oxy C(sp3)-H arylation of cyclic and acyclic ethers. Mechanistic studies suggest that photolysis of a Ni(III) aryl chloride intermediate, generated by photoredox-mediated single-electron oxidation, leads to elimination of a chlorine radical in what amounts to the sequential capture of two photons. Arylations of a benzylic C(sp3)-H bond of toluene and a completely unactivated C(sp3)-H bond of cyclohexane demonstrate the broad implications of this manifold for accomplishing numerous C(sp3)-H bond functionalizations under exceptionally mild conditions.
Shields, Benjamin J.,Doyle, Abigail G.
supporting information
p. 12719 - 12722
(2016/10/13)

Selective chlorination of toluene to p-chlorotoluene catalyzed by nanosized zeolite K-L catalysts
Nanosized zeolite K-L catalysts were synthesized by the hydrothermal method starting from silica sol and potassium aluminate. The crystallinities of the zeolite K-L catalysts increased with increasing the SiO2/Al2O3 mole ratio of reaction solution and prolonging the autoclaving time. Nanosized and well-dispersed zeolite K-L catalysts were synthesized when the SiO2/Al2O3 mole ratio was more than 26:1. Well-crystallized and nanosized zeolite K-L catalysts showed high catalytic activity for the chlorination of toluene to p-chlorotoluene.When the nanosized zeolite K-L catalyst was synthesized with the SiO2/Al2O3 mole ratio of 31:1 at the autoclaving temperature of 150 ?°C for 96 h, the selectivities of p-chlorotoluene and o-chlorotoluene were 76.2% and 20.0%, respectively, at the complete conversion of toluene.
Zhu, Xiaoyan,Fu, Yujun,Yin, Hengbo,Feng, Yonghai,Shen, Lingqin,Wang, Aili,Li, Jitai,Ni, Wenxiu,Xie, Xulan
p. 6150 - 6159
(2015/02/19)

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 0065

(2017/01/02)

Practical and metal-free electrophilic aromatic halogenation by interhalogen compounds generated in situ from N-halosuccinimide and catalytic TMSCL
Halomonochloride compounds (ClCl, BrCl, ICl) generated in situ from N-halosuccinimide and catalytic chlorotrimethylsilane (TMSCl, 0.1 equiv) can efficiently halogenate aromatic compounds to give halogenated products in good to excellent yields and selectivities. The reaction can be carried out at room temperature or at lower temperatures, requires only one hour, is practical to apply to a wide range of substrates, and provides a simple access to a variety of haloarene compounds. Georg Thieme Verlag Stuttgart New York.
Maibunkaew, Tapanee,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Bunrit, Anon,Ruchirawat, Somsak
supporting information
p. 1769 - 1775
(2014/08/05)

Chloroarylation and thiocyanatoarylation of itaconic acid
Under conditions of Meerwein reaction and anionarylation the aryldiazonium salts and itaconic acid form 2-chloro(thiocyanato)-2-benzylbutanedioic acids as the chloro- and thiocyianatoarylation products. The reaction is not accompanied by the decarboxylati
Baranovskii,Petrushka,Fesak,Grishchuk
p. 325 - 328
(2013/08/15)

SMALL MOLECULE MALARIAL ALDOLASE-TRAP ENHANCERS AND GLIDEOSOME INHIBITORS
In one aspect, the present invention relates to a method of identifying compounds useful in modifying the activity of Aldolase. The method includes providing a first model comprising Aldolase or residues of the amino acid sequence corresponding to SEQ ID NO: 1 said residues being at amino acid positions selected from the group consisting of 10-13, 26, 27, 29, 30, 31, 32, 33, 37, 39, 40, 41, 43, 44, 47, 48, 51, 52, 60, 63, 66, 79, 84, 85, 92, 93, 103, 106-109, 112-117, 138, 142, 146, 148, 151, 153, 179, 182, 183, 185, 186, 194, 196, 197, 198, 199, 208, 226-228, 231- 269, 270, 272, 277-283, 285-289, 294, 295, 297-299, 301-304, 306-310, 312, 313, 316, 317, 319, 321, 323, 326, 330, 344, 345, and 347, providing one or more candidate compounds, evaluating contact between the candidate compounds and the first model to determine which of the one or more candidate compounds have an ability to bind to and/or fit in the first model, and identifying compounds which, based on said evaluating, have the ability to bind to and/or fit in the first model as compounds potentially useful for modifying the activity of Aldolase. The present invention also discloses compounds and compositions which modify the activity of Aldolase, or a complex between Aldolase and TRAP. Methods of treating or preventing malaria, or an infection by apicomplexan organisms are also disclosed.
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Page/Page column 74-75

(2013/05/21)

The oxidative halogenations of arenes in water using hydrogen peroxide and halide salts over an ionic catalyst containing sulfo group and hexafluorotitanate
An ionic compound, bis[1-methyl-3-(3′-sulfopropyl)imidazolium] hexafluorotitanate (1), was proved to be the efficient and recyclable catalyst for the oxidative halogenations of arenes in water using H2O 2 as the oxidant and halide salts as the halogenation sources. The mono-halogenated products were obtained selectively by this method. The synergetic catalytic effect coming from the two incorporated functionalities of SO3H and [TiF6]2- was manifested in 1. The halogenation rate catalyzed by 1 was in the ranking of NaBr NaCl > KI. The UV-vis and FT-IR analyses indicated that the successful formation and regeneration of the active peroxo-Ti species (1A) with the aid of proton acid guaranteed the recycling uses of 1.
Wang, Ling,Wang, Sa-Sa,Vo-Thanh, Giang,Liu, Ye
p. 56 - 62
(2013/05/09)

Bronsted acidic ionic liquid accelerated halogenation of organic compounds with N-halosuccinimides (NXS)
The Bronsted-Acidic ionic liquid 1-methyl-3-(4-sulfobutyl) imidazolium triflate [BMIM(SO3H)][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS) under mild conditions with short reaction times. Methyl aryl ketones were converted into a-halo and a,a-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of a-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO3H)][OTf] ionic liquid (IL-A) was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.
Vrazic, Dejan,Jereb, Marjan,Laali, Kenneth K.,Stavber, Stojan
p. 74 - 96
(2013/04/10)

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)

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)

Synthesis of 1H-indazole: A combination of experimental and theoretical studies
A new practical synthesis of 1H-indazole is presented. A previous mechanism for the cyclization step is proved to be nonfeasible and a hydrogen bond propelled mechanism is proposed. The new mechanism is suitable for similar cyclization, and a new reaction is predicted. Springer Science+Business Media B.V. 2012.
Chen, Xinzhi,Zhou, Shaodong,Qian, Chao,He, Chaohong
p. 1619 - 1628
(2012/10/30)

Aromatic substitution in ball mills: Formation of aryl chlorides and bromides using potassium peroxomonosulfate and NaX
Aryl chlorides and bromides are formed from arenes in a ball mill using KHSO5 and NaX (X = Cl, Br) as oxidant and halogen source, respectively. Investigation of the reaction parameters identified operating frequency, milling time, and the number of milling balls as the main influencing variables, as these determine the amount of energy provided to the reaction system. Assessment of liquid-assisted grinding conditions revealed, that the addition of solvents has no advantageous effect in this special case. Preferably activated arenes are halogenated, whereby bromination afforded higher product yields than chlorination. Most often reactions are regio- and chemoselective, since p-substitution was preferred and concurring side-chain oxidation of alkylated arenes by KHSO5 was not observed. The Royal Society of Chemistry.
Schmidt, Robert,Stolle, Achim,Ondruschka, Bernd
p. 1673 - 1679
(2013/02/22)

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)

Copper-catalyzed chlorination of functionalized arylboronic acids
"Chemical Equation Presented" A mild, efficient, Cu(I)-catalyzed method for the conversion of arylboronic acids to aryl chlorides Is reported. This method is particularly useful for the conversion of electron-deficient arylboronic acids to aryl chlorides, a transformation that is inefficient In the absence of Cu catalysis.
Wu, Hong,Hynes Jr., John
supporting information; experimental part
p. 1192 - 1195
(2010/04/27)

Phosphonium nitrate ionic liquid catalysed electrophilic aromatic oxychlorination
Trioctylmethylphosphonium nitrate (P8,8,8,1NO3), an ionic liquid made via a green synthesis, catalyses electrophilic aromatic chlorination of arenes with HCl and air at 80 °C. The aromatic oxychlorination is truly catalytic in nitrate, proceeds without added solvents, and uses atmospheric oxygen as oxidant. The extent of chlorination can be controlled to yield selectively mono or dichlorinated products, and the ionic liquid catalyst can be recycled. Dependence of the chlorination rate on HCl and nitrate concentrations as well as on the rate of re-oxidation of the nitrogen intermediates by air, allowed us to propose a reaction mechanism.
Noe, Marco,Perosa, Alvise,Selva, Maurizio,Zambelli, Luca
experimental part
p. 1654 - 1660
(2010/12/19)

Chlorination of aromatic substrates catalyzed by the phthalocyanine complexes
The chlorination of benzene, toluene, and o-xylene with molecular chlorine in the presence of the phthalocyanine complexes of different structures was studied. The transformations of the catalysts during the reaction were investigated.
Ivanov,Tsentalovich,Kogan,Tomilova,Zefirov
experimental part
p. 1676 - 1679
(2011/04/23)

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)

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)

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)

Aromatic chlorination of ω-phenylalkylamines and ω- phenylalkylamides in carbon tetrachloride and α,α,α- trifluorotoluene
The aromatic halogenation of simple alkylbenzenes with chlorine proceeds smoothly in acetic acid but is much less efficient in less polar solvents. By contrast chlorination of ω-phenylalkylamines, such as 3-phenylpropylamine, occurs readily in either acetic acid, carbon tetrachloride or α,α,α-trifluorotoluene, and in the latter solvents gives high proportions of ortho-chlorinated products. These effects are attributable to the involvement of N-chloroamines as reaction intermediates, with intramolecular delivery of the chlorine electrophile. ω-Phenylalkylamides, such as 3-phenylpropionamide, also easily undergo aromatic chlorination in carbon tetrachloride and α,α,α-trifluorotoluene. These reactions generally show a first-order dependence on the substrate concentration, but not on the amount of chlorine. With carbon tetrachloride, very similar reaction rates are observed with chlorine concentrations ranging from 0.1-1.5 M. In α,α,α-trifluorotoluene, the rates reach a plateau at a chlorine concentration of approximately 0.2 M. These features indicate that the reactions proceed via the formation of intermediates which evidence suggests may be the corresponding O-chloroimidates. Irrespective of the mechanistic details, the reactions are remarkably rapid, being faster than analogous reactions in acetic acid and three to four orders of magnitude more rapid than reactions of simple alkylbenzenes in carbon tetrachloride. Therefore, chlorination of the amines and amides may be accomplished without the need for highly polar solvents, added catalysts or large excesses of chlorine, which are often employed for electrophilic aromatic substitutions. Although the use of carbon tetrachloride is becoming increasingly impractical due to environmental concerns, the trifluorotoluene is a suitable alternative. The Royal Society of Chemistry 2006.
O'Connell, Jenny L.,Simpson, Jamie S.,Dumanski, Paul G.,Simpson, Gregory W.,Easton, Christopher J.
p. 2716 - 2723
(2008/02/08)

SELECTIVE OXIDATION OF ORGANIC COMPOUNDS
This invention relates to the selective oxidation of organic compounds. According to the invention organic compounds are selectively oxidized using a peracid or a source of peracid, a transition metal based heterogeneous catalysts and a borate or boric acid in the presence of water. Using the process of the present invention, both excellent conversion and product selectivity maybe obtained.
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Page/Page column 23-24

(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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Page/Page column 17; 18

(2008/06/13)

Facile Synthesis of 2-Bromo-3-fluorobenzonitrile: An Application and Study of the Halodeboronation of Aryl Boronic Acids
A scaleable synthesis of 2-bromo-3-fluorobenzonitrile via the NaOMe-catalyzed bromodeboronation of 2-cyano-6-fluorophenylboronic acid was developed. The generality of this transformation was demonstrated through the halodeboronation of a series of aryl boronic acids. Both aryl bromides and aryl chlorides were formed in good to excellent yields when the corresponding aryl boronic acid was treated with 1,3-dihalo-5,5-dimethylhydantoin and 5 mol % NaOMe.
Szumigala Jr., Ronald H.,Devine, Paul N.,Gauthier Jr., Donald R.,Volante
p. 566 - 569
(2007/10/03)

Paradigm confirmed: The first use of ionic liquids to dramatically influence the outcome of chemical reactions
It has been an unproven paradigm that the choice of which ionic liquid to use in a chemical reaction can have a dramatic effect on the outcome of that chemical reaction. We demonstrate, for the first time, that the reaction of toluene and nitric acid in three different ionic liquids gives rise to three completely different products in high yield. Furthermore, ionic liquids can catalyze these reactions with the only byproduct being water.
Earle, Martyn J.,Katdare, Suhas P.,Seddon, Kenneth R.
p. 707 - 710
(2007/10/03)

A simple, efficient and regioselective oxychlorination of aromatic compounds using ammonium chloride and oxone
A simple, efficient, mild and regioselective method for oxychlorination of aromatic compounds is reported. The electrophilic substitution of chlorine generated in situ from NH4Cl as a chlorine source and oxone as an oxidant is reported for the first time.
Narender,Mohan, K.V.V. Krishna,Srinivasu,Kulkarni,Raghavan
p. 1335 - 1338
(2007/10/03)

Electroreduction of Organic Compounds, 34 [1]. Cathodic Dehalogenation of Chloroarenes with Electron-Donating Substituents
The electrochemical reduction of chlorinated arenes with electron-donating substituents, i.e. chlorotoluenes, -anisoles and -phenols, is studied. Preparative electrolyses are run in various solvent-supporting electrolytes under potentiostatic and galvanostatic conditions at lead or carbon cathodes. A partial and mostly regioselective hydrodechlorination of compounds with two or more chloro substituents is possible under suitable conditions. The replacement of one single chloro substituent, in particular in a para-position, is difficult. Highly toxic and persistent oligochloro derivatives are thus transformed into less problematic compounds with a low degree of chlorination. The chlorine content of real-life materials such as extracts of soil contaminated with chlorinated phenols and Nitrofen can also be significantly decreased by electroreduction.
Kranz, Olaf,Voss, Jürgen
p. 1187 - 1200
(2007/10/03)

Solvolysis of some arenediazonium salts in binary EtOH/H2O mixtures under acidic conditions
We have determined the product distribution, the rate constants for dediazoniation product formation, and the solvolytic rate constants for 2-, 3-, and 4-methylbenzenediazonium ions (2-, 3-, and 4-MBD, respectively) loss in acidic ethanol/water mixtures over the whole composition range by a combination of spectrophotometric (UV/Vis) and high performance liquid chromatography (HPLC) measurements. The observed rate constants (kobs) for substrate loss are equal to those for product formation, and they remain essentially constant (2-MBD) with changing solvent composition but increase by a factor of ≈2 (4MBD) on going from water to 100% EtOH. Up to four dediazoniation products - cresols (ArOH), chlorotoluene (ArCl), methylphenetole (ArOEt), and toluene (ArH) - were detected, depending on the solvent composition; the major dediazoniation products were the ArOH and ArOEt derivatives. The product selectivity (S) of the reaction towards nucleophiles is low and essentially constant with changing solvent composition, and good linear correlations between log kobs and Yc1 (solvent ionizing power) were observed for the three ArN2+ ions. All data are consistent with the rate-determining formation of an aryl cation, which reacts immediately with available nucleophiles. The data suggest that the distribution of neutral and anionic nucleophiles in the neighborhood of the ground state arenediazonium ion remains essentially unchanged upon dediazoniation, the observed product distribution reflecting the concentrations of nucleophiles in their immediate environment (i.e., in the first solvation shells of the arenediazonium ions). Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Pazo-Llorente, Roman,Bravo-Diaz, Carlos,Gonzalez-Romero, Elisa
p. 3421 - 3428
(2007/10/03)

Directly Observed Reductive Elimination of Aryl Halides from Monomeric Arylpalladium(II) Halide Complexes
Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3/
Roy, Amy H.,Hartwig, John F.
p. 13944 - 13945
(2007/10/03)

Continuous-flow generation of anhydrous diazonium species: Monolithic microfluidic reactors for the chemistry of unstable intermediates
Monolithic microfluidic reactors for the safe, expedient, and continuous synthesis of products involving unstable intermediates were fabricated and assessed. The formation of diazonium salts in anhydrous conditions and their subsequent in situ chlorination within microfiuidic channels under hydrodynamic pumping regimes is presented. Significant enhancements in yield were observed due to enhanced heat and mass transfer in microfluidic systems. Analysis performed using off-line GC and GC-MS was compared with on-line, on-chip Raman spectroscopy for the direct determination of analytes.
Fortt, Robin,Wootton, Robert C. R.,De Mello, Andrew J.
p. 762 - 768
(2013/09/05)