- Efficiency of lithium cations in hydrolysis reactions of esters in aqueous tetrahydrofuran
-
Lithium cations were observed to accelerate the hydrolysis of esters with hydroxides (KOH, NaOH, LiOH) in a water/tetrahydrofuran (THF) two-phase system. Yields in the hydrolysis of substituted benzoates and aliphatic esters using the various hydroxides were compared, and the effects of the addition of lithium salt were examined. Moreover, it was presumed that a certain amount of LiOH was dissolved in THF by the coordination of THF with lithium cation and hydrolyzed esters even in the THF layer, as in the reaction by a phase-transfer catalyst.
- Harada, Yumi,Hayashi, Kazuhiko,Ichimaru, Yoshimi,Imai, Masanori,Kojima, Yuki,Maeda, Azusa,Nakayama, Kanae,Sugiura, Kirara
-
p. 581 - 594
(2021/06/06)
-
- Bimetallic Cooperative Catalysis for Decarbonylative Heteroarylation of Carboxylic Acids via C-O/C-H Coupling
-
Cooperative bimetallic catalysis is a fundamental approach in modern synthetic chemistry. We report bimetallic cooperative catalysis for the direct decarbonylative heteroarylation of ubiquitous carboxylic acids via acyl C-O/C-H coupling. This novel catalytic system exploits the cooperative action of a copper catalyst and a palladium catalyst in decarbonylation, which enables highly chemoselective synthesis of important heterobiaryl motifs through the coupling of carboxylic acids with heteroarenes in the absence of prefunctionalization or directing groups. This cooperative decarbonylative method uses common carboxylic acids and shows a remarkably broad substrate scope (>70 examples), including late-stage modification of pharmaceuticals and streamlined synthesis of bioactive agents. Extensive mechanistic and computational studies were conducted to gain insight into the mechanism of the reaction. The key step involves intersection of the two catalytic cycles via transmetallation of the copper–aryl species with the palladium(II) intermediate generated by oxidative addition/decarbonylation.
- Liu, Chengwei,Ji, Chong-Lei,Zhou, Tongliang,Hong, Xin,Szostak, Michal
-
supporting information
p. 10690 - 10699
(2021/04/09)
-
- Method for preparing iodo-benzoic acid (ester) by improving moral Michael reaction
-
The invention discloses a method for preparing iodo-benzoic acid (ester) by improving a moral reaction, and belongs to the technical field of organic synthesis. The method comprises the following steps: preparing and separating the diazonium tetrafluoroborate through diazotization of aminobenzoic acid (ester) and then performing iodination reaction with the iodinated reagent in an organic medium to obtain the corresponding iodo carboxylic acid (ester). The iodo-benzoic acid (ester) prepared by the method has high purity. The method has the advantages of good quality and simple post-treatment, and the product yield reaches 70 - 90%.
- -
-
-
- Method for preparing aromatic carboxylic acid compound
-
The invention discloses a method for preparing an aromatic carboxylic acid compound. The method comprises the following steps: 1) heating carbon dioxide and hydrosilane in the presence of a copper catalyst in a reaction medium A; and 2) adding a reaction medium B, aryl halide, a palladium catalyst and a base to the reaction mixture in the step 1), sealing the reaction system, and performing a heating reaction. The method has the advantages that raw materials are simple and easy to obtain, the raw materials are cheap and stable, the catalyst is common, easy to obtain and stable, the reaction conditionsaremild, the aftertreatment is simple, the yield is high, and the like.
- -
-
Paragraph 0085-0086; 0103-0105; 0175
(2020/02/14)
-
- CARDIAC SARCOMERE INHIBITORS
-
Provided are compounds of Formula (I), or a pharmaceutically acceptable salt thereof, wherein R1, R2A, R2B, R3, R4, and R5 are as defined herein. Also provided is a pharmaceutically acceptable composition comprising a compound of Formula (I), or a pharmaceutically acceptable salt thereof. Also provided are methods of using a compound of Formula (I), or a pharmaceutically acceptable salt thereof.
- -
-
Paragraph 0525
(2020/03/23)
-
- Highly-chemoselective step-down reduction of carboxylic acids to aromatic hydrocarbons: Via palladium catalysis
-
Aryl carboxylic acids are among the most abundant substrates in chemical synthesis and represent a perfect example of a traceless directing group that is central to many processes in the preparation of pharmaceuticals, natural products and polymers. Herein, we describe a highly selective method for the direct step-down reduction of carboxylic acids to arenes, proceeding via well-defined Pd(0)/(ii) catalytic cycle. The method shows a remarkably broad substrate scope, enabling to direct the classical acyl reduction towards selective decarbonylation by a redox-neutral mechanism. The utility of this reaction is highlighted in the direct defunctionalization of pharmaceuticals and natural products, and further emphasized in a range of traceless processes using removable carboxylic acids under mild, redox-neutral conditions orthogonal to protodecarboxylation. Extensive DFT computations were conducted to demonstrate preferred selectivity for the reversible oxidative addition and indicated that a versatile hydrogen atom transfer (HAT) pathway is operable.
- Liu, Chengwei,Qin, Zhi-Xin,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
-
p. 5736 - 5742
(2019/06/18)
-
- Preparation method of substituted benzoic acid compounds
-
The invention relates to the field of production of chemical products, in particular to a preparation method of substituted benzoic acid compounds represented as general formula (II) in the description. The preparation method comprises steps as follows: corresponding substituted alkyl benzene represented as general formula (I) in the description is taken as a raw material, dilute nitric acid is taken as a reaction medium, oxygen is taken as an oxidant, an imide compound with a structure represented as formula (III) in the description or formula (IV) in the description is selected as a catalyst, all materials are subjected to catalytic oxidation in a high-pressure kettle, and substituted benzoic acid is prepared, wherein R1 is C1-C4 alkyl and R2 is halogen, nitryl, C1-C4 alkyl, methoxyl andtrifluoromethyl. The green preparation method of the substituted benzoic acid compounds is provided and has the advantages of high production purity, simple preparation, mild reaction conditions, simple aftertreatment, low cost and no pollution.
- -
-
Paragraph 0046; 0047
(2019/05/08)
-
- Method for copper-catalyzed carboxylation reaction of arylboronic acid and carbon dioxide
-
The invention discloses a method for a copper-catalyzed carboxylation reaction of arylboronic acid and carbon dioxide. According to the method, carbon dioxide is used as a C1 source, copper catalysisis adopted, alkoxide serves as alkali, and a reaction is carried out in an organic solvent; the method is simple in process and easy to implement, and shows wide functional group compatibility; the method allows various arylboronic acids such as monosubstituted or polysubstituted phenylboronic acid, polycyclic aromatic hydrocarbon boronic acid and benzoheterocyclic boronic acid to be converted into corresponding arylcarboxylic acids with considerable yield under mild conditions; and the produced carboxylic acids have important application value, and can be used for deriving a great number of other common chemical substances, such as acyl halide, acid anhydride, ester and amide.
- -
-
Paragraph 0043; 0044
(2019/12/29)
-
- A simple and efficient iodination of aromatic compounds using I2/Choline Chloride/K2S2O8
-
A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of molecular iodine, choline chloride and potassium peroxodisulfate at 65 °C in acetonitrile. The rate of conversion of aromatic compounds into iodoaromatic compounds was promoted by in situ formed choline peroxodisulfate. This protocol provides an efficient access to iodoarenes with operational simplicity, good functional group tolerance and a moderate to good product yield.
- Parthiban,Joel Karunakaran
-
p. 1659 - 1663
(2018/06/12)
-
- Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
-
A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
- Mukhopadhyay, Sushobhan,Batra, Sanjay
-
supporting information
p. 14622 - 14626
(2018/09/21)
-
- N-Iodosuccinimide (NIS) in Direct Aromatic Iodination
-
N-Iodosuccinimide (NIS) in pure trifluoroacetic acid (TFA) offers a time-efficient and general method for the iodination of a wide range of mono- and disubstituted benzenes at room temperature, as demonstrated in this paper. The starting materials were generally converted into mono-iodinated products in less than 16 hours at room temperature, without byproducts. A few deactivated substrates needed addition of sulfuric acid to increase the reaction rate. Another exception was methoxybenzenes that preferentially were iodinated by NIS in acetonitrile with only catalytic amounts of TFA.
- Bergstr?m, Maria,Suresh, Ganji,Naidu, Veluru Ramesh,Unelius, C. Rikard
-
p. 3234 - 3239
(2017/06/21)
-
- Ligand-Free Palladium-Catalyzed Hydroxycarbonylation of Aryl Halides under Ambient Conditions: Synthesis of Aromatic Carboxylic Acids and Aromatic Esters
-
Aryl halides were readily converted into their corresponding aromatic carboxylic acids in high yields with high selectivity by ligand-free palladium-catalyzed hydroxycarbonylation at room temperature and atmospheric pressure. The new method is operationally simple and scalable. In addition, aromatic esters were easily synthesized through one-pot hydroxycarbonylation/alkylation with alkyl halides.
- Han, Wei,Jin, Fengli,Zhou, Qing
-
p. 1861 - 1868
(2015/06/30)
-
- POLYMER PRECURSORS OF RADIOLABELED COMPOUNDS, AND METHODS OF MAKING AND USING THE SAME
-
One aspect of the present invention relates to novel compounds that can be used to prepare radiolabeled compounds in an effective manner. A second aspect of the present invention relates to a method of synthesizing radiolabeled compounds.
- -
-
Paragraph 0241
(2015/09/23)
-
- Nucleophilic aromatic cine-substitution of hydrogen: The ionic liquid-promoted von Richter reaction
-
Conversion of 4-R-nitrobenzenes into 3-R-benzoic acids under the action of KCN in the EtOH-H2O mixture (the von Richter reaction) is significantly accelerated by ionic liquids thus allowing to extend the scope of the reaction. The finding is pi
- Epishina, Margarita A.,Kulikov, Alexander S.,Ignat'ev, Nikolai V.,Schulte, Michael,Makhova, Nina N.
-
-
- Metal-free iodination of arylboronic acids and the synthesis of biaryl derivatives
-
A simple, general and efficient method is developed for the metal-free iodination of arylboronic acids. The protocol uses very cheap molecular iodine as the halide source and potassium carbonate as the base. The method is highly tolerant of various functional groups present in the substrates. Importantly, the iodination strategy can also be applied very effectively in the one-pot, two-step synthesis of biaryl derivatives. Georg Thieme Verlag Stuttgart New York.
- Niu, Liting,Zhang, Hao,Yang, Haijun,Fu, Hua
-
supporting information
p. 995 - 1000
(2014/05/06)
-
- Trifluoromethylation of arenediazonium salts with fluoroform-derived CuCF3 in aqueous media
-
A new protocol has been developed for trifluoromethylation of arenediazonium salts with moisture-sensitive CuCF3 (from fluoroform) in aqueous media. The reaction is governed by a radical mechanism, tolerates a broad variety of functional groups, and is applicable to the synthesis of complex, polyfunctionalized molecules. This journal is the Partner Organisations 2014.
- Lishchynskyi, Anton,Berthon, Guillaume,Grushin, Vladimir V.
-
supporting information
p. 10237 - 10240
(2014/08/18)
-
- Is carbon dioxide able to activate halogen/lithium exchange?
-
The unexpected effect of carbon dioxide on halogen-lithium exchange (HLE) reactions of selected haloarenes with tBuLi was investigated. In an aliphatic hydrocarbon solvent (pentane), the HLE does not occur at ca. -70 C but, surprisingly, pouring the mixture of reactants onto dry ice and subsequent aqueous acidic hydrolysis gave carboxylic acids resulting from the quench of the first-formed aryllithiums with carbon dioxide. This suggests that CO 2 acts as a promoter of the HLE and, subsequently, serves as an electrophile to trap the aryllithium intermediates that are generated in situ. Theoretical DFT calculations were used to develop a plausible mechanism for the reaction, which indicates that CO2 is a much weaker donor than tetrahydrofuran (THF) so the cleavage of inert tBuLi cubic tetramers into more reactive solvated dimeric species (tBuLi)2(CO2) 4 is disfavored by 42.8 kJ per mol of (tBuLi)4. It is possible that this deaggregation process occurs to some extent when a large excess of CO2 is used. Copyright
- Durka, Krzysztof,Lulinski, Sergiusz,Dabrowski, Marek,Serwatowski, Janusz
-
p. 4562 - 4570
(2014/08/05)
-
- BIOTIN STANNANE FOR HPLC-FREE RADIOIODINATION
-
The present teachings provide methods that enable the preparation and purification of radioiodinated vectors without the need for HPLC purification, as well as novel precursors which include biotin-like substituents useful in such methods.
- -
-
Paragraph 0128; 0129; 0130
(2013/10/08)
-
- 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)
-
- Nickel-catalysed aromatic Finkelstein reaction of aryl and heteroaryl bromides
-
A fast and efficient nickel-catalysed iodination reaction of aryl and heteroaryl bromides has been developed. The transformation was found to be general for a wide range of substrates and was used for the synthesis of iodo-PK11195, an imaging agent of Alzheimer's disease and iniparib, a compound used in the treatment of breast cancer.
- Cant, Alastair A.,Bhalla, Rajiv,Pimlott, Sally L.,Sutherland, Andrew
-
supporting information; experimental part
p. 3993 - 3995
(2012/06/05)
-
- Regioselective iodination of aromatic compounds with potassium iodide in the presence of benzyltriphenylphosphonium perchlorate
-
A simple and efficient method for the selective iodination of various aromatic compounds by using potassium iodide in the presence of benzyltriphenylphosphonium perchlorate, is reported. This method provides several advantages such as good selectivity between ortho and para positions of aromatic compounds and high yields of the products.
- Albadi, Jalal,Abedini, Masoumeh,Iravani, Nasir
-
experimental part
p. 261 - 264
(2012/05/07)
-
- 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)
-
- 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)
-
- Green oxidation of methylarenes to benzoic acids with bromide/bromate in water
-
An efficient and convenient procedure has been developed for the oxidation of methylarenes to the corresponding benzoic acids using a bromide/bromate-based reagent system in water. Regeneration and reusability of the bromide/bromate reagent is demonstrated.
- Patil, Rajendra D.,Bhadra, Sukalyan,Adimurthy, Subbarayappa,Ranu, Brindaban C.
-
experimental part
p. 2922 - 2929
(2010/11/05)
-
- INHIBITORS OF STEAROYL-COA DESATURASE
-
Provided herein are compounds of the formula (I): as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful for the treatment of diseases such as, for example, obesity.
- -
-
-
- Tetraalkylammonium dichloroiodates as iodinating agents: Absence of activity in solid phases and superelectrophilic activity in sulfuric acid
-
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
-
p. 401 - 404
(2008/09/20)
-
- Direct synthesis of iodoarenes from aromatic substrates using molecular iodine
-
Easy laboratory procedures for oxidative iodination of aromatic substrates are presented. One procedure includes the iodination using molecular iodine, concentrated sulfuric acid, and potassium peroxodisulfate, and another uses a reagent system containing molecular iodine, potassium peroxodisulfate, and trifluoroacetic acid. These procedures are especially effective for benzene and less deactivated aromatic substrates, such as halobenzenes, trifluoromethylbenzene, and benzoic acid. Georg Thieme Verlag Stuttgart.
- Hossain, Md. Delwar,Oyamada, Juzo,Kitamura, Tsugio
-
p. 690 - 692
(2008/09/21)
-
- Preparation and X-ray structures of 3-[bis(trifluoroacetoxy)iodo]benzoic acid and 3-[hydroxy(tosyloxy)iodo]benzoic acid: New recyclable hypervalent iodine reagents
-
(Chemical Equation Presented) Preparation, structural characterization, and reactivity of 3-[bis(trifluoroacetoxy)iodo]benzoic acid and 3-[hydroxy-(tosyloxy)iodo]benzoic acid, new recyclable iodine(III) reagents derived from 3-iodosylbenzoic acid, are described. The reduced form of these reagents, 3-iodobenzoic acid, can be easily recovered from the reaction mixtures using ion-exchange resin or basic aqueous workup followed by acidification with HCl.
- Yusubov, Mekhman S.,Funk, Tatyana V.,Chi, Ki-Whan,Cha, Eun-Hye,Ghyung, Hwa Kim,Kirschning, Andreas,Zhdankin, Viktor V.
-
p. 295 - 297
(2008/09/17)
-
- 1,3-Diiodo-5,5-dimethylhydantoin-An efficient reagent for iodination of aromatic compounds
-
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
-
p. 1291 - 1296
(2008/03/27)
-
- Superactivity and dual reactivity of the system N-iodosuccinimide-H 2SO4 in the iodination of deactivated arenes
-
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
-
p. 1278 - 1281
(2008/03/27)
-
- Oxidative iodination of deactivated arenes in concentrated sulfuric acid with I2/NaIO4 and KI/NaIO4 iodinating systems
-
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
-
p. 1195 - 1199
(2007/10/03)
-
- A convenient procedure for the iodination of arenes
-
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
-
p. 575 - 576
(2007/10/03)
-
- A new strategy for preparing molecular imaging and therapy agents using fluorine-rich (fluorous) soluble supports
-
A convenient new strategy for producing radiolabeled compounds in high effective specific activity was developed using soluble fluorous supports. The reported methodology involves a fluorous linker group that is released from the substrate of interest upon reaction with radioiodine. The desired product can then be selectively separated from unreacted starting material and reaction byproducts using a simple fluorous solid-phase extraction procedure. The utility of this approach was demonstrated by labeling a series of benzoic acid derivatives which are commonly used to prepare molecular imaging agents. All compounds were produced in high radiochemical yields, purities, and effective specific activities. The strategy was further elaborated in that it was used to prepare a small collection of radiolabeled benzamides as a way of demonstrating the potential utility of this method for creating libraries of molecular imaging agents. Copyright
- Donovan, Amanda,Forbes, Jane,Dorff, Peter,Schaffer, Paul,Babich, John,Valliant, John F.
-
p. 3536 - 3537
(2007/10/03)
-
- Eco-friendly oxidative iodination of various arenes with sodium percarbonate as the oxidant http://www.mdpi.org
-
Six easy laboratory procedures are presented for the oxidative iodination of various aromatics, mostly arenes, with either molecular iodine or potassium iodide (used as the sources of iodinating species, I+ or I 3+), in the presence of sodium percarbonate (SPC), a stable, cheap, easy to handle, and eco-friendly commercial oxidant.
- Zielinska, Agnieszka,Skulski, Lech
-
p. 1307 - 1317
(2007/10/03)
-
- A Novel Aromatic Iodination Method, with Sodium Periodate Used as the Only Iodinating Reagent
-
Benzene, halobenzenes and some deactivated arenes readily reacted in anhydrous NaIO4/AcOH/Ac2O/concd. H2SO4 mixtures to afford, after quenching with excess aqueous Na2SO3 solution (a reducing agent), purified iodinated products in 27-88 percent yields. This novel method of aromatic iodination is simple, fairly effective and environmentally safe.
- Lulinski, Piotr,Sosnowski, Maciej,Skulski, Lech
-
p. 671 - 675
(2007/10/03)
-
- An aromatic iodination method, with iodic acid used as the only iodinating reagent
-
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
-
p. 394 - 400
(2007/10/03)
-
- COPPER-CATALYZED FORMATION OF CARBON-HETEROATOM AND CARBON-CARBON BONDS
-
One aspect of the present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-sulfur bond between the sulfur atom of a thiol moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper(II)-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-carbon bond between the carbon atom of cyanide ion and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In another embodiment, the present invention relates to a copper-catalyzed method of transforming and aryl, heteroaryl, or vinyl iodide. Yet another embodiment of the present invention relates to a tandem method, which may be practiced in a single reaction vessel, wherein the first step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl iodide from the corresponding aryl, heteroaryl, or vinyl chloride or bromide; and the second step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl nitrile, amide or sulfide from the aryl, heteroaryl, or vinyl iodide formed in the first step.
- -
-
-
- Chemical Manganese Dioxide (CMD): Its application to the oxidative iodination of benzene, halobenzenes and some deactivated arenes
-
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
-
p. 595 - 601
(2007/10/03)
-
- Eco-friendly Oxidative Iodination of Various Arenes with a Urea-Hydrogen Peroxide Adduct (UHP) as the Oxidant
-
Three easy eco-friendly laboratory procedures are presented for the oxidative iodination of various activated and deactivated arenes with molecular iodine, in the presence of UHP (percarbamide), a stable, strongly H-bonded, solid urea-hydrogen peroxide adduct as the oxidant.
- Lulinski, Piotr,Kryska, Anna,Sosnowski, Maciej,Skulski, Lech
-
p. 441 - 445
(2007/10/03)
-
- Easy, inexpensive and effective oxidative iodination of deactivated arenes in sulfuric acid
-
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
-
p. 9113 - 9119
(2007/10/03)
-
- Methods for purifying radiolabelled compounds
-
One aspect of the present invention relates to a method of purifying radiolabelled compounds comprising a) loading onto a fluorous polymer a radiolabelled compound precursor comprising a fluoroalkyl tin moiety; b) reacting the radiolabelled compound precursor with a radiolabel delivering compound to give a radiolabelled compound, wherein the fluoroalkyl tin moiety is replaced by a radiolabel; and c) eluting the radiolabelled compound from the fluorous polymer.
- -
-
Page/Page column 8; 21
(2008/06/13)
-
- Palladium(II)-catalyzed sequential hydroxylation-carboxylation of biphenyl using formic acid as a carbonyl source
-
(Equation Presented) A simultaneous hydroxylation-carboxylation of biphenyl occurred to give 4′-hydroxy-4-biphenylcarboxylic acid, which has wide potential application as a polyester monomer.
- Shibahara, Fumitoshi,Kinoshita, Shinsuke,Nozaki, Kyoko
-
p. 2437 - 2439
(2007/10/03)
-
- Iodination of aromatic compounds with iodine and n-butyltriphenylphosphonium peroxodisulfate
-
Iodine and n-butyltriphenylphosphonium peroxodisulfate can be successfully used for the iodination of some aromatic compounds in acetonitrile as solvent. The yields obtained are good to excellent.
- Tajik,Esmaeili,Mohammadpoor-Baltork,Ershadi,Tajmehri
-
p. 1319 - 1323
(2007/10/03)
-
- Tetramethylammonium dichloroiodate: An efficient and environmentally friendly iodination reagent for iodination of aromatic compounds under mild and solvent-free conditions
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Tetramethylammonium dichloroiodate (1, TMADCI) as a mild and efficient iodination reagent was prepared. Iodination of different aromatic compounds with this reagent takes place fast and with high yields under solvent-free conditions.
- Hajipour, Abdol R.,Arbabian, Marty,Ruoho, Arnold E.
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p. 8622 - 8624
(2007/10/03)
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- Iodination of both deactivated and activated arenes with sodium periodate or sodium iodate as the oxidants
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Five easy, relatively inexpensive, and environmentally-safe aromatic oxidative iodination procedures are presented; three of them are particularly suitable for deactivated arenes. Nine deactivated arenes, four halobenzenes, benzene, toluene, and N,N-dimethylaniline were reacted upon with the following anhydrous systems: diiodine/NaIO4 or (in four cases) NaIO3/acetic anhydride/glacial acetic acid, acidified with varying amounts of concd (98%) sulfuric acid; the following workups are explained. The aromatic oxidative iodination reactions proceeded mostly at room temperature and within 1-8 h to give fifteen mono- and two diiodinated purified products (sometimes obtained in 2-3 different ways) in 51-95% yields.
- Lulinski, Piotr,Skulski, Lech
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p. 951 - 956
(2007/10/03)
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- 2,4,6,8-Tetraiodoglycoluril in sulfuric acid as a new powerful reagent for iodination of deactivated arenes
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Deactivated arenes are iodinated readily at 0°C by the action of 2,4,6,8-tetraiodoglycoluril in sulfuric acid to give the iodoarenes in generally good yields. (C) 2000 Elsevier Science Ltd.
- Chaikovski,Filimonov,Yagovkin,Kharlova
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p. 9101 - 9104
(2007/10/03)
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- Oxidative iodination of arenes with manganese(IV) oxide or potassium permanganate as the oxidants
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Novel and easy laboratory methods (novel Procedures 1-4) are presented for the oxidative mono- and diiodination of both activated and deactivated arenes, which gave the pure iodinated products in 62-89% yields. The reactions were carried out in the anhydrous, strongly acidic system, I2/activated MnO2/AcOH/Ac2O/concd H2SO4, firstly at r.t. for 2 h, then at 45-55 °C for 2-9 h. The resulting mixtures were poured into excess aq Na2SO3 solution buffered with (NH4)2CO3 to neutralize H2SO4. The following workups are given. Similarly, on carrying out the iodination reactions (at 35 °C, for one hour) in the anhydrous, strongly acidic system, I2/KMnO4/AcOH/Ac2O/concd H2SO4, it was possible to mono- or diiodinate several deactivated arenes in 73-87% yields (improved Procedures 5 and 6).
- Lulinski, Piotr,Skulski, Lech
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p. 115 - 120
(2007/10/03)
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