- Visible light-mediated, high-efficiency oxidation of benzyl to acetophenone catalyzed by fluorescein
-
An environmentally friendly aerobic oxidation of benzyl C(sp3)-H bonds to ketones via selective oxidation catalysis was developed. Fluorescein is an efficient photocatalyst with excellent chemical selectivity. The reaction has a wide substrate scope, and a successful gram-scale experiment demonstrated its potential industrial utility.
- Geng, Haoxing,Liu, Xin,Zhu, Qing
-
supporting information
(2021/12/20)
-
- Halogen Bonding Tetraphenylethene Anion Receptors: Anion-Induced Emissive Aggregates and Photoswitchable Recognition
-
A series of tetraphenylethene (TPE) derivatives functionalized with highly potent electron-deficient perfluoroaryl iodo-triazole halogen bond (XB) donors for anion recognition are reported. 1H NMR titration experiments, fluorescence spectroscopy, dynamic light scattering measurements, TEM imaging and X-ray crystal structure analysis reveal that the tetra-substituted halogen bonding receptor forms luminescent nanoscale aggregates, the formation of which is driven by XB-mediated anion coordination. This anion-coordination-induced aggregation effect serves as a powerful sensory mechanism, capable of luminescence chloride sensing at parts per billion concentration. Furthermore, the doubly substituted geometric isomers act as unprecedented photoswitchable XB donor anion receptors, where the composition of the photostationary state can be modulated by the presence of a coordinating halide anion.
- Beer, Paul D.,Davis, Jason J.,Docker, Andrew,Kuhn, Heike,Langton, Matthew J.,Shang, Xiaobo,Yuan, Daohe,Zhang, Zongyao
-
supporting information
p. 19442 - 19450
(2021/07/31)
-
- PROCESS FOR THE PREPARATION OF DIHALOBENZOPHENONES, NEW CHEMICALS USEFUL FOR ITS IMPLEMENTATION AND METHODS FOR PREPARING SAID CHEMICALS
-
The invention relates to new compounds of formulae (IV) and (VII): (IV) (VII) wherein X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine and R is a hydrocarbyl radical, said compounds being useful as precursors and/or intermediates for the preparation of 4,4'dihalobenzophenones of formula (I): (I) wherein X is as defined above.
- -
-
-
- NEW CYCLOADDUCT PRECURSORS OF DIHALOBENZOPHENONES AND PREPARATIONS THEREOF
-
The invention relates to new compounds of formula (I): wherein X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine, which are useful for the preparation of 4,4'dihalobenzophenones of formula (III): wherein X is as defined above.
- -
-
Page/Page column 12-13
(2019/06/17)
-
- Method for preparing symmetric diarylketone through catalytic oxidative carbonylation
-
The invention discloses a method for preparing symmetric diarylketone of a formula (I) as shown in the description. The method comprises the following steps: mixing arylboronic acid (II) (Ar-B(OH)2 (II)), a palladium catalyst, a promoter and an organic solvent in a reactor, introducing air and CO having a volume ratio of (7-19):1, reacting under the conditions of a pressure of 1-6 atm and a temperature of 30-80 DEG C for 8-16 hours, and performing after-treatment on the reaction solution, thereby obtaining the product symmetric diarylketone. According to the method disclosed by the invention,the air directly serves as an oxidizing agent to replace the O2 to be applied to oxidative carbonylation of the arylboronic acid, and the ratio of the air to CO is beyond an explosion limit. Therefore, the catalytic system is safe and economic. The palladium catalyst is small in dosage and simple in separation and can be recycled for several times. The method disclosed by the invention is mild inreaction condition, excellent in substrate suitability and high in yield.
- -
-
Paragraph 0023; 0024; 0025; 0026; 0029
(2019/03/08)
-
- SPIROCYCLIC DERIVATIVE, AND POLYMER, MIXTURE, FORMULATION AND ORGANIC ELECTRONIC DEVICE COMPRISING THE SAME
-
Provided are a spirocyclic derivative, and a high polymer, a mixture, a composition and an organic electronic device containing same, wherein in the spirocyclic derivative, two spirocyclic units are directly or indirectly connected by a sp3 hybridized carbon atom, thus effectively adjusting the energy level of the compound, and being beneficial for improving the photoelectric performance of the compound and the stability of the device. An effective solution is provided for effectively reducing the manufacturing cost and improving the efficiency and lifetime of a light-emitting device.
- -
-
Paragraph 0177; 0180; 0181
(2019/01/04)
-
- Palladium-Catalyzed Carbonylative Homocoupling of Aryl Iodides for the Synthesis of Symmetrical Diaryl Ketones with Formic Acid
-
A convenient method for the palladium-catalyzed carbonylative homocoupling of aryl iodides was developed. With formic acid as the CO source, various symmetrical diaryl ketones were synthesized in moderate to good yield in the presence of a palladium catalyst.
- Wu, Fu-Peng,Peng, Jin-Bao,Qi, Xinxin,Wu, Xiao-Feng
-
p. 173 - 177
(2017/11/27)
-
- ELECTRO-OPTICAL DEVICE AND USE THEREOF
-
The present invention relates to an electro-optical device comprising a) an anode, b) a cathode, c) at least one emitter layer, which is arranged between the anode and the cathode, containing at least one semi-conductive, organic material, and d) at least one intermediate layer, which is arranged between the at least one emitter layer and the anode, and which contains a polymer having hole-conducting structural units. The device is characterized in that the polymer having hole-conducting structural units additionally have structural units having electron-conducting properties. The devices according to the invention have significantly longer service lives compared to known devices.
- -
-
Paragraph 0215-0218
(2016/12/01)
-
- Co(III)-Catalyzed Synthesis of Quinazolines via C-H Activation of N-Sulfinylimines and Benzimidates
-
C-H activation of arenes has been established as an important strategy for heterocycle synthesis via annulations between arenes and unsaturated coupling partners. However, nitriles failed to act as such a coupling partner. Dioxazolones have been employed as a synthon of nitriles, and subsequent coupling with arenes such as N-sulfinylimines and benzimidates bearing a functionalizable directing group provided facile access to two classes of quinazolines under Co(III)-catalysis.
- Wang, Fen,Wang, He,Wang, Qiang,Yu, Songjie,Li, Xingwei
-
supporting information
p. 1306 - 1309
(2016/04/01)
-
- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
-
Provided is a compound which is represented by chemical formula 1, wherein the compound exhibits high luminous efficiency and low driving voltage and increases lifespan of a device. Also, provided are an organic electric element using the same and an electronic device thereof.
- -
-
Paragraph 0153; 0194
(2016/10/31)
-
- Synthesis and photochromic properties of a bis(diarylethene)-naphthopyran hybrid
-
The synthesis and photochromic properties of a triphotochromic molecule consisting of one naphthopyran flanked by two diarylethene units investigated by UV-Visible and Nuclear Magnetic Resonance spectroscopies are reported. Six different states resulting from the open/closed naphthopyran associated with one or two open/cyclized diarylethenes have been characterized. The photochemical and thermal interconversion between the six states of the triphotochromic target was followed allowing to determine the existing pathways upon irradiation with 313 and 365 nm light excitation, and during thermal evolution. Switching of the naphthopyran group is possible, independently of the state of the diarylethene groups. However, the diarylethene groups cannot be closed if the naphthopyran group is open.
- Erko, Firealem G.,Cseh, Liliana,Berthet, Jér?me,Mehl, Georg H.,Delbaere, Stéphanie
-
p. 102 - 109
(2015/03/05)
-
- Understanding the guanidine-like cationic moiety for optimal binding into the DNA minor groove
-
Based on our previous positive results with bis-guanidine-like diaromatic compounds as DNA minor groove binders, we propose a new family: bis-2-amino-1,4,5,6-tetrahydropyrimidines. According to calculated parameters, these dicationic systems would have a more suitable size and lipophilicity for binding into the minor groove than previous series. Moreover, their DFT-optimised structures and docking into an AT oligomer model show that they would bind in the minor groove with good strength and without energy penalty. Hence, we prepared compounds 4 a-c and evaluated their binding to ssDNA and poly(dA-dT)2 by thermal denaturation experiments. The results showed that 4 a (CO) and 4 d (NH) were the best DNA binders. Compared to the previous series, 4 a-d are better binders than bis-guanidiniums but poorer than bis-2-aminoimidazolinium derivatives. Moreover, circular dichroism experiments using ssDNA and poly(dA-dT)2 confirmed binding into the minor groove. Based on our computational design as well as biophysical studies, we have been able to determine that the optimal interaction of guanidine-like dications in the minor grove occurs with bis-2-aminoimidazolinium systems.
- O'Sullivan, Patrick,Rozas, Isabel
-
supporting information
p. 2065 - 2073
(2014/11/07)
-
- Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids and CO: A highly selective approach to diaryl ketones
-
A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O2, which makes this method practical for further applications.
- Ren, Long,Jiao, Ning
-
supporting information
p. 2411 - 2414
(2014/10/15)
-
- Rh-catalyzed carbonylation of arylzinc compounds yielding symmetrical diaryl ketones by the assistance of oxidizing agents
-
Carbonylative homocoupling of arylzinc compounds 1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was achieved in the presence of Rh-dppf catalyst, affording symmetrical diaryl ketones in good yields. Under similar conditions, Pd or Ni catalysts induced oxidative homocoupling of 1 to yield biaryls instead. The beneficial catalysis by Rh in the carbonylation was presumed to stem from the facility by which the migration of the aryl ligand to CO at the Rh3+ intermediate occurred.
- Kobayashi, Kana,Nishimura, Yugo,Gao, Fuxing,Gotoh, Kazuma,Nishihara, Yasushi,Takagi, Kentaro
-
supporting information; experimental part
p. 1949 - 1952
(2011/06/20)
-
- Modulation of spectrokinetic properties of o-quinonoid reactive intermediates by electronic factors: Time-resolved laser flash and steady-state photolysis investigations of photochromic 6- and 7-arylchromenes
-
A ready synthetic accessibility of a series of 6- and 7-arylchromenes via Pd0-catalyzed Suzuki coupling protocol has permitted a comprehensive investigation of the thermal decay behavior of a broad set of photogenerated o-quinonoid reactive intermediates. It is shown that substantial mesomeric effect between the benzopyran nucleus and the aryl ring at C6 or C7 position of the former renders significant absorption beyond 350 nm such that they are readily photoactivated to yield colored o-quinonoid intermediates. The absorption spectra of the latter are found to be strongly influenced by the substituents on C2-, C6- and C7-aryl rings; indeed the colored absorptions can be conveniently tuned by appropriate choice of substituents. The thermal decay (bleaching phenomenon), which is important from the point of view of their application in ophthalmic lenses, was investigated in each case by μs-ms as well as real-time absorption spec-troscopy. By careful experimentation, we have extracted the decay rate constants for Z,E and E,E o-quinonoid isomers of all 6- and 7-arylchromenes in an attempt to establish a correlation between the electronic attributes with their thermokinetic behavior. From a combined analysis of μs-ms (laser flash) and real-time kinetic data, it is shown that the colored o-quinonoid intermediates decay faster when the C2-aryl and C6-/C7-aryl rings contain electron-donating and electron-accepting groups, respectively. In the same vein, the decay was found to occur slowly for the reversed scenario, while intermediate decay rates are observed when both substituents are electron-donating. Thus, any substituent on the C2-aryl ring that contributes mesomerically to the development of charge on the quinonoid oxygen, and any substituent on the C6-/C7-aryl ring that exerts -I effect appear to expedite thermal decay. Furthermore, evidence is obtained for the first time from μs time-resolved laser-flash spectroscopy for the formation and characterization of the trans,cis (E,Z) o-quinonoid isomer, which has heretofore eluded spectral characterization in the photochromic phenomena of pyrans.
- Moorthy, Jarugu Narasimha,Koner, Apurba L.,Samanta, Subhas,Roy, Ankur,Nau, Werner M.
-
supporting information; experimental part
p. 4289 - 4300
(2009/12/07)
-
- Mapping the active site in a chemzyme: Diversity in the N-substituent in the catalytic asymmetric aziridination of imines
-
(Chemical Equation Presented) The active site of the aziridination catalyst derived from either the VANOL or VAPOL ligand and B(OPh)3 is larger than expected and can accommodate not only significant substitution on the diarylmethyl unit of the imine but also that alkyl (but not perfluorylalkyl) substituents on the aryl groups lead to enhanced rates and enantioselection. The screen of diarylmethyl N-substituents on the imine revealed that the 3,5-di-tert-butyldianisylmethyl group (BUDAM) gave exceptionally high asymmetric inductions for imines of aryl aldehydes.
- Zhang, Yu,Lu, Zhenjie,Desai, Aman,Wulff, William D.
-
supporting information; experimental part
p. 5429 - 5432
(2009/06/20)
-
- Triaryl methane derivatives as antiproliferative agents
-
Clotrimazole (CLT) 1, a synthetic anti-fungal imidazole derivative, inhibits tumor cell proliferation and angiogenesis. In the current study, flow cytometric analysis demonstrated that the decrease in tumor cell growth by CLT 1 was associated with inhibition of cell cycle progression at the G 1-S phase transition, resulting in G0-G1 arrest. A series of CLT 1 analogues has been generated in order to develop CLT 1 derivatives that are devoid of the imidazole moiety which is responsible for the hepatoxicity associated with CLT 1 while retaining CLT 1 efficacy. The majority of these analogues demonstrate in vitro antiproliferative activity ranging from submicromolar to micromolar concentrations.
- Al-Qawasmeh, Raed A.,Lee, Yoon,Cao, Ming-Yu,Gu, Xiaoping,Vassilakos, Aikaterini,Wright, Jim A.,Young, Aiping
-
p. 347 - 350
(2007/10/03)
-
- Hypervalent iodine in synthesis. 83. Palladium-catalyzed carbonylative coupling of diaryliodonium salts mediated by indium
-
In the presence of palladium catalyst and indium diaryl-iodonium salt; react with carbon monoxide under mild reaction conditions to give diaryl ketone; in moderate yields.
- Zhou, Tao,Chen, Zhen-Chu
-
p. 3431 - 3435
(2007/10/03)
-
- Polymer electrolyte and process for producing the same
-
A polymer electrolyte having, in a main chain, a structural unit represented by the following formula (1):-[Ar1-(SO2-N-(X+)-SO2-Ar2)m-SO2-N-(X+)-SO2-Ar1-O]- wherein Ar1 and Ar2 independently represent a divalent aromatic groups, m represents an integer of 0 to 3, and X+ represents an ion selected from hydrogen ion, an alkali metal ion and ammonium ion, which is excellent in proton conductivity, thermal resistance and strength. The polymer electrolyte is soluble in solvents and has excellent film forming property and recycling efficiency.
- -
-
-
- Kinetics and Mechanism of the Methyltrioxorhenium-Catalyzed Sulfoxidation of Thioketones and Sulfines
-
Kinetic studies have been carried out on the oxidation of thiobenzophenones and thiocamphor by hydrogen peroxide and on the second step in the sequence, oxidation of the resulting sulfines (Ar2C= S=O). The first reaction follows the pattern now common to methyltrioxorhenium/H2O2 reactions, in that the rate constant for the reaction between the peroxorhenium intermediate and the thioketone follows a Hammett correlation such that electron-releasing substrates react more rapidly. The reaction constant is p = -1.12. However, the plot of log(kX/kH) for the sulfines against 2σ, determined over the range -1.6 2 under these conditions rather than undergoing disproportionation to SO2 and S. Also, SO was trapped with a 1,3-diene as a thiophene-1-oxide.
- Huang, Ruili,Espenson, James H.
-
p. 6374 - 6376
(2007/10/03)
-
- Electrochemical Synthesis of Symmetrical Ketones from Acid Chlorides
-
The electrochemical reduction of aroyl or arylacetyl chlorides was performed in an undivided cell fitted with a stainless steel anode and a nickel foam cathode.The electrolyses were carried out at constant current in acetonitrile as solvent, leading to the corresponding symmetrical ketones. Key words: symmetrical ketones synthesis, acid chloride electroreduction.
- Folest, Jean-Claude,Pereira-Martins, Edouard,Troupel, Michel,Perichon, Jacques
-
p. 7571 - 7574
(2007/10/02)
-
- FUNCTIONALISATION OF SATURATED HYDROCARBONS. PART XVII. REACTIVITY OF CARBON-CARBON DOUBLE BONDS.
-
The Gif oxidation systems cleave methylidene olefins into the ketone or aldehyde and formaldehyde.This is considered to be a further manifestation of an Fe oxenoid species.Similarly, more substituted olefins are oxidized to the corresponding unsaturated ketones or aldehydes.The oxidation of limonene afforded the ketone 24 resulting from methylene cleavage and racemic carvone 25.The latter is considered to originate from a symmetrical ?-allyl complex of iron.
- Barton, Derek H. R.,Lee, Kyu Wan,Mehl, Wolf,Ozbalik, Nubar,Zhang, Li
-
p. 3753 - 3768
(2007/10/02)
-
- Novel electron-accepting compound and method for preparing the same
-
An electron-accepting compound represented by the formula (I): STR1 wherein R represents a hydrogen atom or --B(Mes)2 and Mes represents a mesityl group. A method for preparing an electron-accepting compound represented by the above-described formula (I), which comprises condensing a benzophenone derivative represented by the following formula (II) with malononitride, STR2 wherein R and Mes have the same meanings as defined for the formula (I).
- -
-
-
- Kinetics and Mechanism of the Oxidation of Some Substituted Benzhydrols by Aqueous Bromine
-
Oxidation of substituted benzhydrols by aqueous bromine has been found to be first order with respect to both, the oxidant and substrate benzhydrol.The activation parameters have been evaluated.A tentative for the mechanism oxidation of benzhydrols by bromine has been proposed which is consistent with the experimental data.
- Ameta, R.C.,Suresh, K.S.,Shanker, R.
-
p. 502 - 506
(2007/10/02)
-
- CATALYTIC CARBONYLATION OF DIARYLIODONIUM SALTS PROMOTED BY PALLADIUM-ZINC SYSTEM. A NEW SYNTHESIS OF DIARYL KETONES AND DIARYL-α-DIKETONES
-
Diaryliodonium salts react with carbon monoxide, in the presence of zinc and a catalytic amount of palladium acetate, to give a mixture of the corresponding diaryl ketones and diaryl-α-diketones under mild conditions.
- Uchiyama, Masaharu,Suzuki, Takehiko,Yamazaki, Yasuo
-
p. 1201 - 1202
(2007/10/02)
-
- Unsymmetrical Ketone Synthesis via Palladium Catalyzed Carbonylation of Organic Halides
-
Aryl alkyl (or benzyl) ketones are selectively prepared by the reaction of aryl iodides and alkyl iodides (or benzyl chlorides) in the presence of a stoichiometric amount of zinc-copper couple and a catalytic amount of palladium(O) complex under an atmospheric pressure of carbon monoxide.
- Tamaru, Yoshinao,Ochiai, Hirofumi,Yamada, Yoshimi,Yoshida, Zen-ichi
-
p. 3869 - 3872
(2007/10/02)
-
- Merostabilization in radical ions, triplets, and biradicals. 4. Substituent effects on the half-wave reduction potentials and n, ?* triplet energies of aromatic ketones
-
The half-wave reduction potentials, measured by cyclic voltammetry, and n, ?* triplet energies, measured by phosphorescence spectroscopy, were determined for a series of eighteen symmetrically and unsymmetrically substituted benzophenones.Attempts are made to correlate the results with Hammett substituent constants.Better correlations are observed when the data are correlated with a two-parameter function consisting of Hammett substituent constants and a set of substituent parameters describing variations in free radical stability.Significant deviations from "normal" behaviour are observed for benzophenones substituted by both electron-donating and electron-withdrawing substituents.These deviations are attributed to merostabilization of the radical-like species, and an empirical approach designed to evaluate the importance of this effect is developed.Ab initio calculations of molecular orbital energies in meta- and para-substituted benzaldehydes are used to evaluate the substituent effects on E1/2red and ETn,?* in terms of the effect on the energies of the n- and ?*-orbitals.
- Leigh, William J.,Arnold, Donald R.,Humphreys, Robert W. R.,Wong, Po Cheong
-
p. 2537 - 2549
(2007/10/02)
-
- Reduction of 2,2-Diaryl-1-nitroethylenes : New Synthesis of 2,2-Diarylacetaldehydes and 1,1,4,4-Tetraarylbuta-1,3-dienes
-
2,2-Diarylacetaldehydes (VII) have been obtained by selective and controlled reduction of 2,2-diaryl-1-nitroethylenes (IV) in acid medium, and also by acid hydrolysis of 2,2-diarylvinyl-N-acetamides (VI).Nitroalkenes (IV) have been prepared by the reaction of 2,2-diarylethylenes (I) with nitrous acid whereas N-acetamide derivatives (VI) have been obtained by reductive acetylation of the nitro compounds (IV).A number of 1,1,4,4-tetraarylbuta-1,3-dienes (XI) have been obtained by the condensation of 2,2-diarylacetaldehydes (VII) with appropriate 2,2-diarylethylenes (I).Structures of the products have been assigned on the basis of analytical data and chemical and spectral evidences.
- Tadros, Wadie,Awad, Sami B.,Sakla, Alfy B.,Abdul-Malik, Nadia F.,Armanious, Emili R.
-
p. 199 - 202
(2007/10/02)
-