- Low-temperature and highly efficient liquid-phase catalytic nitration of chlorobenzene with NO2: Remarkably improving the para-selectivity in O2-Ac2O-Hβ composite system
-
In this work, we developed a low-temperature and efficient approach for the highly selective preparation of valuable p-nitrochlorobenzene from the liquid-phase catalytic nitration of chlorobenzene with NO2 in O2-Ac2O-Hβ composite system. The results demonstrated that the introduction of molecular oxygen remarkably enhanced the chlorobenzene conversion and the cooperation catalysis of Hβ zeolite and Ac2O envidently improved the selectivity to para-nitro product. Under the optimized reaction conditions, 93.6 % of the selectivity to p-nitrochlorobenzene with 84.0 % of chlorobenzene conversion was obtained, and the ratio of p-nitrochlorobenzene to o-nitrochlorobenzene could reach up to 20.3. Furthermore, the selectivity distribution of nitration products was reasonably explained by the density functional theory (DFT) calculation. Finally, the possible nitration reaction pathway of chlorobenzene with NO2 was suggested in O2-Ac2O-Hβ composite catalytic system. The present work affords a new and mild nitration approach for highly selective preparation of valuable para-nitro products, and has potential industrial application prospects.
- Deng, Renjie,Liu, Pingle,Luo, He'an,Ni, Wenjin,You, Kuiyi,Zhao, Fangfang
-
-
- Synthesis of 4-substituted azopyridine-functionalized Ni(II)-porphyrins as molecular spin switches
-
We present the synthesis and the spin switching efficiencies of Ni(II)-porphyrins substituted with azopyridines as covalently attached photoswitchable ligands. The molecules are designed in such a way that the azopyridines coordinate to the Ni ion if the azo unit is in cis configuration. For steric reasons no intramolecular coordination is possible if the azopyridine unit adopts the trans configuration. Photoisomerization of the azo unit between cis and trans is achieved upon irradiation with 505 nm (trans→cis) and 435 nm (cis→trans). Concurrently with the isomerization and coordination/decoordination, the spin state of the Ni ion switches between singlet (low-spin) and triplet (high-spin). Previous studies have shown that the spin switching efficiency is strongly dependent on the solvent and on the substituent at the 4-position of the pyridine unit. We now introduced thiol, disulfide, thioethers, nitrile and carboxylic acid groups and investigated their spin switching efficiency.
- Herges, Rainer,Ludwig, Jannis,Moje, Tobias,R?hricht, Fynn
-
p. 2589 - 2597
(2020/11/26)
-
- Pd-Catalyzed Decarboxylative Ortho-Halogenation of Aryl Carboxylic Acids with Sodium Halide NaX Using Carboxyl as a Traceless Directing Group
-
A highly regioselective Pd-catalyzed carboxyl directed decarboxylative ortho-C-H halogenation of cheap o-nitrobenzoic acids with NaX (X = I, Br) under aerobic conditions has been established. The utility of the method has been demonstrated by the gram-scale reaction and derivatization of the product. Experimental results have confirmed Pd and Bi played critical roles in the transformation and indicated the transformation might proceed via 2-halo-6-nitrobenzoic acid derivative intermediate.
- Fu, Zhengjiang,Jiang, Yongqing,Wang, Shuiliang,Song, Yuanyuan,Guo, Shengmei,Cai, Hu
-
supporting information
p. 3003 - 3007
(2019/05/10)
-
- ipso-Bromination/iodination of arylboronic acids: Poly(4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents
-
Poly(4-vinyl pyridine) supported bromine/iodine complexes were prepared and probed for ipso-bromination/iodination of arylboronic acids. These solid complexes with catalytic amount of additive are found to be safe and efficient reagent system for the ipso-bromination/iodination. The reaction occurs under mild conditions and tolerates various functional groups resulting in products with high selectivity and yields.
- Fu, Fang,Gurung, Laxman,Czaun, Miklos,Mathew, Thomas,Prakash, G.K. Surya
-
supporting information
(2019/08/26)
-
- An efficient gram scale synthesis of aryl iodides from aryl diazofluoroborates in water under mild conditions
-
Transition metal-free synthesis of synthetically valuable aryl iodides from aryl diazofluroborates in water under mild conditions has been described. Majority of synthesized aryl iodides are obtained in quantitative yields (>99%) under present reaction conditions. The structural effects due to the substituents present on aryl diazofluoroborates did not show any satisfactory effect on the yields of the aryl iodides. Hence, the methodology presented here was found to be adventitious for the quantitative production of synthetically valuable aryl iodides.
- Gholap, Somnath S.
-
p. 594 - 599
(2018/06/26)
-
- Compound having dual effects on 5-HT and application thereof in treatment of depression
-
The invention discloses a compound having dual effects on 5-HT and application thereof in treatment of depression. As shown in the description, R1, R2, R3 and R4 are independently selected from H, F or CH3. In recent years, a dual-effect anti-depression drug with partial excitation of serotonin 1A receptor and selective serotonin reuptake inhibition becomes a hot spot for new antidepressant research. In rat synaptosome, [3H]5-HT uptake inhibition and h5-HT1A binding affinity experiments prove that the compound has 5-HT reuptake inhibition effect and 5-HT1A receptor excitation effect, indicating that the compound can be used as a medicament for treating central nervous system dysfunction such as depression and anxiety in humans.
- -
-
Paragraph 0028; 0029; 0030; 0031
(2018/09/21)
-
- Compound having dual functions to 5-HT and application thereof in depressive disorder treatment
-
The invention discloses a compound having dual functions to 5-HT and application thereof in depressive disorder treatment. The formula is shown in the description, wherein R1, R2, R3 and R4 are independently selected from H, F or OH. In recent years, an antidepressant having the dual functions of 5-hydroxytryptamine 1A acceptor partial agitation and selective 5-hydroxytryptamine re-uptake inhibition becomes a hot point direction of a novel antidepressant drug research. In a [3H]5-HT uptake inhibiting effect experiment of a rat synaptosome and a h5-HT1A combined affinity experiment, the compound is verified to have the 5-HT re-uptake inhibiting effect and the agitating effect to a 5-HT1A acceptor. The fact that the compound can be used as a drug for treating human central nervous system disorders, such as a depressive disorder and an anxiety disorder, is demonstrated.
- -
-
Paragraph 0028-0031
(2018/10/19)
-
- Drug for treating depression
-
The invention discloses a drug for treating depression. The formula is as shown in the specification, wherein R1, R2 and R3 are independently selected from H, F or OCH3. In recent years, 5-serotonin 1A receptor partly excited and selective 5-serotonin reuptake inhibition of the dual role of antidepressants become a hot research focus of novel antidepressants. (H) 5-HT uptake inhibition experiment and h5-HT1A binding affinity experiment in rat synapse show that the compound has 5-HT reuptake inhibition and activating effect on 5-HT1A receptors, and the compound can serve as the drug for treating human central nervous system dysfunction like depression and anxiety.
- -
-
Paragraph 0028; 0029; 0030; 0031
(2018/10/19)
-
- A medicament for the treatment of depression (by machine translation)
-
The invention discloses a method for treating depression, Wherein: R1 , R2 , R3 , R4 Independently selected from the group of H, or CH F3 . In recent years, 5 - hydroxytryptamine 1 A receptor partial agonistic and selective 5 - hydroxytryptamine reuptake inhibition with dual function of antidepressant has become anti-depression pharmaceutical research and in the direction of the hot spots. In the RAT synapsis body to [3 H] 5 - HT uptake inhibition experiment and h5 - HT1 A In the experiment confirmed that the binding affinity of the compounds of the invention have 5 - HT reuptake inhibiting effect and to 5 - HT1 A Receptor agonistic, note the compounds of this invention can be used as treatment of human central nervous system dysfunction such as depression, anxiety neurosis. (by machine translation)
- -
-
Sheet 0027; 0028; 0029; 0030
(2018/10/19)
-
- A medicament for the treatment of depression (by machine translation)
-
The invention discloses a method for treating depression, Wherein: R1 , R2 , R3 , R4 Independently selected from the group of H, F or OH. In recent years, 5 - hydroxytryptamine 1 A receptor partial agonistic and selective 5 - hydroxytryptamine reuptake inhibition with dual function of antidepressant has become anti-depression pharmaceutical research and in the direction of the hot spots. In the RAT synapsis body to [3 H] 5 - HT uptake inhibition experiment and h5 - HT1 A In the experiment confirmed that the binding affinity of the compounds of the invention have 5 - HT reuptake inhibiting effect and to 5 - HT1 A Receptor agonistic, note the compounds of this invention can be used as treatment of human central nervous system dysfunction such as depression, anxiety neurosis. (by machine translation)
- -
-
Paragraph 0028; 0029; 0030; 0031
(2018/10/19)
-
- Metathesis-active ligands enable a catalytic functional group metathesis between aroyl chlorides and aryl iodides
-
Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals—aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C–P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.
- Lee, Yong Ho,Morandi, Bill
-
p. 1016 - 1022
(2018/09/06)
-
- Visible-Light-Induced Decarboxylative Iodination of Aromatic Carboxylic Acids
-
A convenient, efficient and practical visible-light-induced decarboxylative iodination of aromatic carboxylic acids has been developed, and the corresponding aryl iodides were obtained in good yields. The method shows some advantages including the use of readily available aromatic carboxylic acids as the starting materials, simple and mild conditions, high efficiency, wide substrate scope and tolerance of various functional groups.
- Jiang, Min,Yang, Haijun,Jin, Yunhe,Ou, Lunyu,Fu, Hua
-
supporting information
p. 1572 - 1577
(2018/06/26)
-
- Rapid Iododeboronation with and without Gold Catalysis: Application to Radiolabelling of Arenes
-
Radiopharmaceuticals that incorporate radioactive iodine in combination with single-photon emission computed tomography imaging play a key role in nuclear medicine, with applications in drug development and disease diagnosis. Despite this importance, there are relatively few general methods for the incorporation of radioiodine into small molecules. This work reports a rapid air- and moisture-stable ipso-iododeboronation procedure that uses NIS in the non-toxic, green solvent dimethyl carbonate. The fast reaction and mild conditions of the gold-catalysed method led to the development of a highly efficient process for the radiolabelling of arenes, which constitutes the first example of an application of homogenous gold catalysis to selective radiosynthesis. This was exemplified by the efficient synthesis of radiolabelled meta-[125I]iodobenzylguanidine, a radiopharmaceutical that is used for the imaging and therapy of human norepinephrine transporter-expressing tumours.
- Webster, Stacey,O'Rourke, Kerry M.,Fletcher, Conor,Pimlott, Sally L.,Sutherland, Andrew,Lee, Ai-Lan
-
supporting information
p. 937 - 943
(2017/12/26)
-
- 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)
-
- Method for synthesizing m-iodonitrobenzene compound
-
Provided is a method for synthesizing m-iodonitrobenzene; in the presence of oxygen gas, a palladium catalyst, a copper additive, a bismuth reagent and potassium phosphate, an o-nitrobenzoic acid compound and metal iodide are subjected to a substitution reaction in an organic solvent to form a corresponding m-iodonitrobenzene compound, wherein a metal in the metal iodide is an alkali metal or an alkaline earth metal. The method has obvious advantages of cheap and easily obtained reaction raw materials (including o-nitrobenzoic acid and MI), small amount of the metal catalyst, minimum environmental pollution with oxygen gas as an oxidant, good tolerance on various functional groups on an aromatic ring and the like. The method can be widely applied in the fields of synthesis of drugs, materials, natural products and the like in industrial and academic circles.
- -
-
Paragraph 0093-0094
(2018/03/24)
-
- Easy Access to Difluoromethylene-Containing Arene Analogues through Palladium-Catalysed C–H Olefination
-
An efficient palladium-catalysed ortho-C–H olefination of α,α-difluorophenylacetic acid derivatives using 8-aminoquinoline as a bidentate directing group has been developed. A range of olefinated arenes can thus be synthesized in a concise way. This reaction provides an easy and straightforward route to a panel of difluoromethylated arene analogues in moderate to good yields, with a satisfactory tolerance of common functional groups. Transformation of the products into a variety of other difluoromethylene-containing compounds demonstrates the utility of this method.
- Shao, Changdong,Shi, Guangfa,Zhang, Yanghui
-
supporting information
p. 5529 - 5538
(2016/11/25)
-
- 3-production of aniline
-
PROBLEM TO BE SOLVED: To provide a method for producing a 3-halogenated aniline, by which useful high purity 3-iodoaniline can be produced in a good yield.SOLUTION: The method for producing a 3-halogenated aniline is characterized by precipitating an acid salt of the 3-halogenated aniline by treating a 3-halogenated aniline isomer mixture containing the 3-halogenated aniline and at least one regioisomer of the 3-halogenated aniline with an acid in a solvent. Preferably, the acid is hydrochloric acid or phosphoric acid.
- -
-
Paragraph 0023
(2018/08/30)
-
- Copper-mediated aerobic iodination and perfluoroalkylation of boronic acids with (CF3)2CFI at room temperature
-
The copper-mediated aerobic reactions between the branched (CF3)2CFI and boronic acids (R-B(OH)2) are described. Different from the linear perfluoroalkyl analogs CF3(CF2)nI (n?=?2, 3, 5, 7), (CF3)2CFI reacting with R-B(OH)2at room temperature under air in the presence of catalytic Cu powder provided exclusively the corresponding iodides (R-I), while the aerobic reactions of arylboronic acids with (CF3)2CFI at room temperature in the presence of Cu(OAc)2gave the perfluoroalkylation products (R-CF(CF3)2) in acceptable to moderate yields. The iodination reaction could be further promoted by hydroquinone, the addition of which improved the oxidation ability of (CF3)2CFI and provided the ipso-iodination products in high yields. The perfluoroalkylation was facilitated by the copper carboxylates since the addition of these salts into the reaction mixtures could successfully give rise to Ar-CF(CF3)2.
- Liu, Xi-Hai,Leng, Jing,Jia, Su-Jiao,Hao, Jian-Hong,Zhang, Fanglin,Qin, Hua-Li,Zhang, Cheng-Pan
-
-
- PROCESS FOR THE PREPARATION OF N-IODOAMIDES
-
The present invention provides new stable crystalline N-iodoamides - 1-iodo- 3,5,5-trimethylhydantoin (1-ITMH) and 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO). The present invention further provides a process for the preparation of organic iodides using N-iodoamides of this invention and recovery of the amide co-products from waste water.
- -
-
Paragraph 00234-00235
(2015/05/26)
-
- Practical and efficient ipso-iodination of arylboronic acids via KF/I2 system
-
A facile and effective iododeboronation of variously substituted aryl and heteroarylboronic acids through activation and subsequent ipso-introduction of iodine is presented. The use of KF and I2 at 80 °C in 1,4-dioxane furnishes iodinated compounds in high yields.
- Tramutola, Francesco,Chiummiento, Lucia,Funicello, Maria,Lupattelli, Paolo
-
p. 1122 - 1123
(2015/02/19)
-
- A practical and general ipso iodination of arylboronic acids using N-iodomorpholinium iodide (NIMI) as a novel iodinating agent: mild and regioselective synthesis of aryliodides
-
A mild and efficient protocol for the ipso-iodination of aryl boronic acids using N-iodomorpholinium iodide (NIMI) generated in situ from morpholine and molecular iodine as a novel iodinating agent has been developed. The addition of a catalytic amount of copper iodide found to promote rate enhancement of the iodination reaction and dramatic increase in the yield depending upon the nature of the boronic acid was observed. The mechanistic study revealed that depending upon the nature of the substrate, either the classical ipso substitution or copper catalysed iododeborylation pathway overall dominates the present iodination reaction. The features such as mild reaction conditions, operational simplicity, high to excellent yields, excellent functional group compatibility and low catalyst loading make this method potentially useful in organic synthesis.
- Tale,Toradmal,Gopula
-
p. 84910 - 84919
(2015/10/28)
-
- Regioselective nitration of aromatics with nanomagnetic solid superacid SO42-/ZrO2-MxOy-Fe 3O4 and its theoretical studies
-
A series of micro- and nanosulfated zirconia loaded on Fe3O 4 or other metal oxides (SO42-/ZrO 2-MxOy-Fe3O4 (M=Ti 4+, V5+, and Zn2+)) was prepared, characterized, and used in nitration. The nitration conditions with these solid superacids were then optimized to achieve the best regioselectivity and improve the performances of the catalysts as well. In the experimental results, SZTF (SO42-/ZrO2-TiO2-Fe 3O4) showed excellent catalytic activity and it increased the surface area of SO42-/ZrO2 by up to 15 %. The increase not only facilitated the generation of NO2+, but also provided more opportunities for metal ions to interact with aromatic compounds. With chlorobenzene as substrate, theoretical research on its geometric parameters, electron clouds, and electron spin density was used to investigate the interaction between transition metals and chlorobenzene.
- Wang, Peng Cheng,Zhu, Jie,Liu, Xiang,Lu, Ting Ting,Lu, Ming
-
p. 310 - 317
(2013/08/23)
-
- Halogenation and DNA cleavage via thermally stable arenediazonium camphorsulfonate salts
-
A series of stable arenediazonium camphorsulfonate salts (2a-2j) were synthesized by simple diazotization of several aromatic amines in the presence of sodium nitrite and camphorsulfonic acid. All the new arenediazonium camphorsulfonates, which were characterized by multinuclear (1H and 13C) NMR, IR, DSC, and X-ray diffraction analysis (2e and 2f) provide unambiguous proof for the molecular structures of 2e and 2f. The efficient application of these salts in halogenation reactions was studied in solvent and solvent-free conditions and the DNA cleavage activity was also assessed. These arenediazonium camphorsulfonate salts are noticed as efficient DNA cleaving agents.
- Vajpayee, Vaishali,Moon, Mi Eun,Lee, Sunmi,Ravikumar, Sambandam,Kim, Hyunuk,Ahn, Byungchan,Choi, Seoyoon,Hong, Soon Ho,Chi, Ki-Whan
-
p. 3511 - 3517
(2013/04/23)
-
- Iron-catalyzed cross-coupling reaction: Recyclable heterogeneous iron catalyst for selective olefination of aryl iodides in poly(ethylene glycol) medium
-
An environmentally friendly iron-based catalyst supported on acac-functionalized silica was successfully prepared and evaluated as a heterogeneous catalyst for Mizoroki-Heck reaction of aryl iodides and olefins. Our catalytic system showed good activities that were comparable to that of palladium catalysts. The catalyst was simply recovered from the reaction mixture and recycled five times. Furthermore, the reaction was carried out in poly(ethylene glycol) as a green solvent. Interestingly, using this catalyst, aryl iodides were selectively olefinated in the presence of aryl bromides.
- Hajipour, Abdol Reza,Azizi, Ghobad
-
supporting information
p. 1030 - 1034
(2013/07/26)
-
- Palladium-catalyzed arylation of simple arenes with iodonium salts
-
The development of an arylation protocol for simple arenes with diaryliodonium salts using the Herrmann-Beller palladacycle catalyst is reported. The reaction takes simple aromatic feedstocks and creates valuable biaryls for use in all sectors of the chem
- Storr, Thomas E.,Greaney, Michael F.
-
supporting information
p. 1410 - 1413
(2013/05/09)
-
- Sterically controlled iodination of arenes via iridium-catalyzed C-H borylation
-
A mild method to prepare aryl and heteroaryl iodides by sequential C-H borylation and iodination is reported. The regioselectivity of this process is controlled by steric effects on the C-H borylation step and is complementary to existing methods to form aryl iodides. The iodination of boronic esters has potential for the synthesis of radiolabeled aryl iodides, as demonstrated by the concise synthesis of a potential tracer for SPECT imaging.
- Partridge, Benjamin M.,Hartwig, John F.
-
supporting information
p. 140 - 143
(2013/03/28)
-
- A simple and effective copper catalyst for the conversion of arylboronic acids to aryl iodides at room temperature
-
Simple Cu(NO3)2·3H2O was demonstrated to be of ability to catalyze the conversion of arylboronic acids to aryl iodides at room temperature. Compared with the previous copper-catalyzed method, the present procedure avoids the use of the ligand, the oxidant as well as the heating condition.
- Ren, Yun-Lai,Tian, Xin-Zhe,Dong, Chuanhua,Zhao, Shuang,Wang, Jianji,Yan, Mengjie,Qi, Xiaoguang,Liu, Guihua
-
-
- Tetraflic acid (1,1,2,2-Tetrafluoroethanesulfonic acid, HC 2F4SO3H) and gallium tetraflate as effective catalysts in organic synthesis
-
Tetraflic acid offers ample acidity for various organic reactions that require high acidity. Its gallium(III) salt is an efficient catalyst under mild condtions for synthetic transformations such as the ketonic Strecker reaction for the synthesis of fluorinated α-amino nitriles and condensation- cyclzation reactions using suitable fluoro ketones and 1,2-disubstituted benzenes for the direct preparation of 5-membered or 6-membered fluorinated heterocycles. Copyright
- Prakash, G. K. Surya,Mathew, Thomas,Panja, Chiradeep,Kulkarni, Aditya,Olah, George A.,Harmer, Mark A.
-
p. 2163 - 2171
(2012/11/07)
-
- Halodeboronation of organotrifluoroborates using tetrabutylammonium tribromide or cesium triiodide
-
Halodeboronation of organotrifluoroborates using commercially available tetrabutylammonium tribromide (TBATB) or cesium triiodide in aqueous medium is reported. The mild, transition metal-free method has proven to be tolerant of a wide range of functional groups. High regio- and chemoselectivity are observed. Two synthetic routes to (Z)-dibromoalkenes from alkynes, through stereodefined (Z)-2-bromoalkenyltrifluoroborates and (Z)-1,2-bis(boryl) alkenyltrifluoroborates, have been developed using the TBATB mediated bromodeboronation as the key step.
- Yao, Min-Liang,Kabalka, George W.,Blevins, David W.,Reddy, Marepally Srinivasa,Yong, Li
-
experimental part
p. 3738 - 3743
(2012/06/30)
-
- PROCESS FOR THE PREPARATION OF IODIDES
-
This invention is directed to a process for the preparation of high yield alkyl or aryl iodide from its corresponding carboxylic acid using N-iodo amides.
- -
-
Page/Page column 34
(2012/01/05)
-
- Superelectrophilic iodination of deactivated arenes with triiodoisocyanuric acid
-
The reaction of triiodoisocyanuric acid (TICA) with deactivated arenes in acidic medium led to the efficient and regioselective formation of the corresponding iodoarenes, in 55-88% isolated yield. The acidity of the medium was found to be the most important factor influencing the electrophilic iodination of weakly nucleophilic substrates by TICA. Georg Thieme Verlag Stuttgart New York.
- Da Ribeiro, Rodrigo S.,Esteves, Pierre M.,De Mattos, Marcio C. S.
-
experimental part
p. 739 - 744
(2011/04/24)
-
- Copper-catalyzed halogenation of arylboronic acids
-
In this Letter, a copper-catalyzed halogenation of arylboronic acids was described. This reaction tolerates a variety of functional groups, providing aromatic halides with good yields. It represents a facile and mild procedure to aryl halides.
- Zhang, Guangyou,Lv, Guanglei,Li, Liping,Chen, Fan,Cheng, Jiang
-
experimental part
p. 1993 - 1995
(2011/04/25)
-
- General copper-catalyzed transformations of functional groups from arylboronic acids in water
-
A simple and general copper-catalyzed method has been developed for transformations of various functional groups (i I, i N3, i SO2R, i OH, i NH2, and i NO 2) on aromatic rings from arylboronic acids in water under air. The protocol uses cheap and readily available inorganic salts (KI, NaN3, NaSO2R, NaOH, NaNO2) and aqueous ammonia as the functional-group sources, simple Cu2O/NH3 as the catalyst system, environmentally friendly water as the solvent, and oxygen in air as the oxidant. Importantly, the copper catalyst system in water was recyclable. This study should provide a useful strategy for interconversions of the functional groups on aromatic rings.
- Yang, Haijun,Li, Yong,Jiang, Min,Wang, Junmei,Fu, Hua
-
experimental part
p. 5652 - 5660
(2011/06/23)
-
- Gold-catalysis: Reactions of organogold compounds with electrophiles
-
Different arylgold(I), one alkynylgold(I), and one vinylgold(I) triphenylphosphane complexes were subjected to electrophilic halogenation reagents. With N-chlorosuccinimid, N-bromosuccinimid, and N-iodosuccinimid as well as the Barluenga reagent, selectively halogenated compounds were obtained. Trifluoroacetic acid, as a source of protons, leads to a clean protodeauration. With N-fluorobenzenesulfonimide or Selectfluor, exclusively a homocoupling was observed. For the precursor of the vinylgold(I) complex, a similar oxidative coupling could be induced by gold(III) chloride. Reactions with silicon or tin electrophiles failed. CSIRO 2010.
- Hashmi, A. Stephen K.,Ramamurthi, Tanuja Dondeti,Todd, Matthew H.,Tsang, Althea S.-K.,Graf, Katharina
-
experimental part
p. 1619 - 1626
(2011/09/12)
-
- 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)
-
- Triolborates: water-soluble complexes of arylboronic acids as precursors to iodoarenes
-
A facile synthesis of aryl and heteroaryl iodides from water-soluble complexes of aryl- and heteroarylboronic acids has been developed.
- Akula, Murthy R.,Yao, Min-Liang,Kabalka, George W.
-
experimental part
p. 1170 - 1171
(2010/04/23)
-
- A one-pot method for the iodination of aryl amines via stable aryl diazonium silica sulfates under solvent-free conditions
-
A convenient and rapid one-pot method for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, silica sulfuric acid and potassium iodide under solvent-free conditions at room temperature. Various aromatic amines possessing electron-withdrawing groups or electron-donating groups are converted into the corresponding aryl iodides in good yields. Georg Thieme Verlag Stuttgart.
- Zarei, Amin,Hajipour, Abdol R.,Khazdoozd, Leila
-
experimental part
p. 941 - 944
(2009/12/02)
-
- Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems
-
Iodination of o-nitrotoluene in H2SO4 or CF 3SO3H at 0°C with compounds having a nitrogen-iodine bond leads to the formation of isomeric mono- and diiodo derivatives whose ratio differs from the statistical value. The reaction of nitrobenzene with 2 equiv of N-I reagents in trifluoromethanesulfonic acid at 0°C takes less than 1 min and yields 79-85% of m-iodonitrobenzene. The electrophilic reactivity of the iodinating agents was estimated by quantum-chemical methods.
- Chaikovskii,Filimonov,Funk
-
experimental part
p. 1349 - 1352
(2010/01/11)
-
- Halo- and azidodediazoniation of arenediazonium tetrafluoroborates with trimethylsilyl halides and trimethylsilyl azide and Sandmeyer-type bromodediazoniation with Cu(I)Br in [BMIM][PF6] ionic liquid
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(Chemical Equation Presented) Reaction of [ArN2][BF4] salts immobilized in [BMIM][PF6] ionic liquid (IL) with TMSX (X = I, Br) and TMSN3 represents an efficient method for the preparation of iodo-, bromo-, and azido-derivatives via dediazoniation. The reactions can also be effected starting with ArNH2 by in situ diazotization with [NO][BF4] followed by reaction with TMSX or TMSN3. Depending on the substituents on the benzenediazonium cation, competing fluorodediazoniation (ArF formation) and hydrodediazoniation (ArH formation) were observed. Dediazoniation with TMSN3 and with TMSI generally gave the highest chemoselectivity toward ArN3 and ArI formation. The IL was recycled and reused up to 5 times with no appreciable decrease in the conversions. Multinuclear NMR monitoring of the interaction of [ArN 2][BF4]/TMSX, [BMIM][PF6]/TMSX, and [BMIM][PF6]/TMSX/[ArN2][BF4] indicated that TMSF is formed primarily via [ArN2][BF4]/ TMSX, generating [ArN2][X] in situ, which gives ArX on dediazoniation. Competing formation of ArF in Sandmeyer-type bromodediazoniation of [ArN 2][BF4] with Cu(I)Br immobilized in the IL points to significant involvement of heterolytic dediazoniation.
- Hubbard, Abigail,Okazaki, Takao,Laali, Kenneth K.
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p. 316 - 319
(2008/09/17)
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- Tetraalkylammonium dichloroiodates as iodinating agents: Absence of activity in solid phases and superelectrophilic activity in sulfuric acid
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In contrast to published results, tetraalkylammonium dichloroiodates (Alk4N+ICl2-) cannot be iodinating reagents for arenes in solvent-free conditions. Nevertheless, tetraalkylammonium dichloroiodates in sulfuric acid solutions or in the presence of Ag 2SO4 in H2SO4 possess superelectrophilic properties and act as very convenient and efficient iodinating agents for deactivated arenes. Georg Thieme Verlag Stuttgart.
- Filimonov, Victor D.,Semenischeva, Nadya I.,Krasnokutskaya, Elena A.,Ho, Yun Hwang,Chi, Ki-Whan
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p. 401 - 404
(2008/09/20)
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- Superactivity and dual reactivity of the system N-iodosuccinimide-H 2SO4 in the iodination of deactivated arenes
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Dissolution of N-iodosuccinimide in sulfuric acid gives rise to electrophilic iodine-containing species which are capable of successfully iodinating aromatic compounds with electron-withdrawing substituents in the temperature range from 0 to 20°C. The iodination in sulfuric acid is effected by both protonated N-iodosuccinimide and IOS(O)(OH+)OH intermediate.
- Chaikovskii,Filimonov,Skorokhodov,Ogorodnikov
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p. 1278 - 1281
(2008/03/27)
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- 1,3-Diiodo-5,5-dimethylhydantoin-An efficient reagent for iodination of aromatic compounds
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1,3-Diiodo-5,5-dimethylhydantoin in organic solvents successfully iodinates alkylbenzenes, aromatic amines, and phenyl ethers. The reactivity of electrophilic iodine is controlled by acidity of the medium. Superelectrophilic iodine generated upon dissolution of 1,3-diiodo-5,5-dimethylhydantoin in sulfuric acid readily reacts with electron-deficient arenes at 0 to 20°C with formation of the corresponding iodo derivatives in good yields. The structure of electrophilic iodine species generated from 1,3-diiodo-5,5- dimethylhydantoin in sulfuric acid is discussed.
- Chaikovskii,Filimonov,Funk,Skorokhodov,Ogorodnikov
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p. 1291 - 1296
(2008/03/27)
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- Oxidative iodination of deactivated arenes in concentrated sulfuric acid with I2/NaIO4 and KI/NaIO4 iodinating systems
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Deactivated arenes were mono- or diiodinated with strong electrophilic I+ reagents, which were prepared from NaIO4 and either I2 or KI in concentrated H2SO4 (minimum 95% by weight). In general a small excess of the dark brown iodinating solution was used (1.1/1.5 equivalents, for nitrobenzene two equivalents was required). The iodinations were conducted at 25-30 °C with a reaction time of 1-2 hours using either a 'direct' or an 'inverse' method of aromatic iodination to give mono- or diiodinated pure products in 31-91% optimized yields. Georg Thieme Verlag Stuttgart.
- Kraszkiewicz, Lukasz,Sosnowski, Maciej,Skulski, Lech
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p. 1195 - 1199
(2007/10/03)
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- A convenient procedure for the iodination of arenes
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Two different procedures for the iodination of various arenes using potassium bromate and potassium iodide in the presence of hydrochloric acid are presented. Iodination of benzene, naphthalene and deactivated arenes were carried out in aqueous acetic acid medium and good yields of iodoarenes were obtained. Activated arenes, such as anisole, substituted phenols and anilines underwent excellent conversion to their iodinated products in an aqueous methanol medium.
- Sathiyapriya,Karunakaran, R. Joel
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p. 575 - 576
(2007/10/03)
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- An aromatic iodination method, with iodic acid used as the only iodinating reagent
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Benzene, halobenzenes, and a number of more or less deactivated arenes, including nitrobenzene, readily reacted in anhydrous HIO3/AcOH/ Ac2O/conc. H2SO4 mixtures to probably give ArIO2 intermediates or other hypervalent species (not isolated). The final reaction mixtures were poured into excess aq. Na2SO3 solution (a reductant) to give the purified iodinated products in 39-83% yields.
- Krassowska-Swiebocka, Barbara,Prokopienko, Grazyna,Skulski, Lech
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p. 394 - 400
(2007/10/03)
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- N-halosuccinimide/BF3-H2O, efficient electrophilic halogenating systems for aromatics
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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.
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p. 15770 - 15776
(2007/10/03)
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- Easy, inexpensive and effective oxidative iodination of deactivated arenes in sulfuric acid
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Two 'model' deactivated arenes, benzoic acid and nitrobenzene, were effectively monoiodinated within 1 h at 25-30 °C, with strongly electrophilic I+ reagents, prior prepared from diiodine and various oxidants (CrO3, KMnO4, active MnO2, HIO 3, NaIO3, or NaIO4) in 90% (v/v) concd sulfuric acid (ca. 75 mol% H2SO4). Next, an I2/ NaIO3/90% (v/v) concd H2SO4 exemplary system was used to effectively mono- or diiodinate a number of deactivated arenes. All former papers dealing with the direct iodination of deactivated arenes are briefly reviewed.
- Kraszkiewicz, Lukasz,Sosnowski, MacIej,Skulski, Lech
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p. 9113 - 9119
(2007/10/03)
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- Chemical Manganese Dioxide (CMD): Its application to the oxidative iodination of benzene, halobenzenes and some deactivated arenes
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After comparing our previous and newer results for numerous oxidative aromatic iodination experiments using various brands (of active MnO2 as the oxidants, we recommend the use of a Chemical Manganese Dioxide (Aldrich CMD; 90+% (MnO2) as the oxidant of choice, since it is satisfactorily pure and chemically active, and is notably less costly than other options.
- Lulinski, Piotr,Krassowska-Swiebocka, Barbara,Skulski, Lech
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p. 595 - 601
(2007/10/03)
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