- Poly(spirobifluorene)s containing nonconjugated diphenylsulfone moiety: Toward blue emission through a weak charge transfer effect
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Instead of conjugated dibenzothiophene-S,S-dioxide (DBTSO), we have introduced nonconjugated diphenylsulfone (DPSO) as the electron-deficient unit into the main chain of poly(spirobifluorene)s (PSFs). Because of the weaker electron affinity of DPSO relative to DBTSO, the charge transfer from the pendant 2,3,6,7-tetraoctyloxyfluorene to the main chain can be effectively prevented. Consequently, the resultant polymers containing DPSO moiety show pure blue emissions, which is different from DBTSO-based PSFs that exhibit undesired green emissions. With a single-layer device configuration, a peak luminous efficiency of 2.90 cd/A and a maximum luminescence of 14130 cd/m2 have been realized for the polymer PSFDPSO03. The corresponding CIE coordinates are (0.17, 0.18), nearly independent of the applied current density from 2 to 592 mA/cm2. These results indicate that tuning the electron affinity of the incorporated electron-deficient units is a very promising strategy to control the charge transfer strength for the development of blue-emitting PSFs with high efficiency and stability.
- Wang, Xuchao,Zhao, Lei,Shao, Shiyang,Ding, Junqiao,Wang, Lixiang,Jing, Xiabin,Wang, Fosong
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Read Online
- D–π–A polysulfones for blue electroluminescence
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Donor–π–acceptor type fluorene-based copolymers with a sulfone unit were designed and synthesized for application in efficient pure-blue light emitting. The electroluminescence behaviors of these copolymers were investigated by fabricating light-emitting diodes and electrochemical cell devices. The former device little functioned but the latter worked well. The electrochemical cell devices having a configuration of ITO/PEDOT:PSS/copolymer:ionic liquid/Al exhibited purplish blue electroluminescence with an emission maximum at 434 nm (CIE coordinates (x, y) = (0.17, 0.10)) measured at 7 V. The initial positive scan of the D–π–A polysulfone based light emitting electrochemical cell with a sweep rate of 0.1 V s?1 afforded a maximum luminance of 1080 cd m?2 with a current efficiency of 1.96 cd A?1 at an operating voltage of 12.5 V.
- Geng, ZhongMin,Sato, Go,Marumoto, Kazuhiro,Kijima, Masashi
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Read Online
- Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
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A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
- Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
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supporting information
p. 10314 - 10318
(2021/12/17)
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- Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mechanochemistry
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A variety of substituted diarylsulfones could be synthesized by simple arenes and 3CdSO4·xH2O in the presence of P2O5 under high-speed ball milling. It was suggest the aromatic sulfonation was performed by arene and in situ generated H2SO4, following-up by electrophilic substitution with another arene to give diarylsulfone.
- Qin, Shuai,Zhang, Pu,Qin, Yu-Jun,Guo, Zhi-Xin
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supporting information
(2020/01/06)
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- Bipolar fluorophores based on intramolecular charge-transfer moieties of sulfone for nondoped deep blue solution-processed organic light-emitting diodes
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Dipolar emitters exhibited excellent performance in organic light-emitting diode (OLED). However, these molecules had intramolecular charge-transfer (ICT) properties, which posed challenge to obtain deep blue emission. In this study, three fluorophores were designed by introducing carbazole and diphenylamine as electron donors and sulfone as electron acceptor due to their mild charge-accepting properties and twisted angles. These materials appeared almost in vertical angles of the dihedral configuration, and exhibited high thermal and electrochemical stability, suitable for solution-processed OLED. The solution-processed non-doped devices based on these three emitters were realized, where two emissions within the standard deep blue emission range were achieved with the Commission International e de l'Eclairage (CIE) coordinates of (0.16, 0.12) and (0.16, 0.15).
- Cao, Liang,Zhang, Lei,Wei, Qiang,Zhang, Jiasen,Chen, Dongjun,Wang, Sheng,Su, Shi-jian,Wang, Tao,Ge, Ziyi
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- Synthesis and photophysical properties of fluorescent dyes based on triphenylamine, diphenylamine, diphenyl sulfone or triphenyltriazine derivatives containing an acetylene linkage group
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In this study, ten fluorescent dyes were prepared based on three different kinds of central moiety, such as triphenylamine, diphenylsulfone or triphenyltriazine, which was coupled to either carbazole or naphthalimidinyl group via an acetylene linkage group. N-n-Butyl-carbazole, N-phenyl-carbazole or N-n-butyl-naphthalimide was coupled to the individual central moiety of triphenylamine, diphenyl sulfone, 2,4,6-triphenyl-1,3,5-trazine or diphenylamine using a Sonogashira coupling reaction in the final step. All dyes were confirmed their chemical structure by 1H NMR, GC-Mass and elemental analyses. The absorption properties and thermal stabilities of the fluorescent dyes were examined. Density Functional Theory (DFT) and Time-Dependent DFT calculations were carried out, in addition to geometry simulation, by using the Gaussian 09 program. In terms of fluorescence properties in this series, two dyes based on diphenyl sulfonyl and three dyes based on triphenylamine substituted by 1–3 of N-n-butyl-carbazole exhibited a blue emission, whereas three dyes based on triphenylamine substituted by 1–3 of N-n-butyl-naphthalimide were observed by a red emitter which can be attributable to both effects the bathochromic shifts in absorption maxima and larger Stokes shifts. In case of corresponding 2,4,6-triphenyl-1,3,5-trazine central moiety coupled to a carbazole ring, a green fluorescence was emitted. Results revealed that the fluorescence of the dyes is affected by the electron-donating strength of the acetylene linkages involved in the π-conjugation systems of the dyes.
- Ahn, Sung-Ok,Choi, Jae-Hong,Kim, Kyung-Won,Kwon, Su-Hyeon,Lee, Byung-Jun,Lee, Ju-Hong
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- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
- Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 3048 - 3055
(2019/03/21)
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- Method for photocatalytic synthesis of sulfur sulfone compounds
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The invention discloses a method for photocatalytic synthesis of sulfur sulfone compounds, and belongs to the technical field of catalysis. The invention provides a novel green environmentally-friendly method to efficiently synthesize the sulfur sulfone derivatives, and one thioether compound and an oxidizing agent are subjected to direct oxidization to form one corresponding sulfur sulfone compound under illumination by utilizing cercosporin as a catalyst. The method provided by the invention adopts the cercosporin as the catalyst, the catalytic conditions are milder, the reaction can be performed at room temperature under visible light irradiation, the catalyst has high catalytic activity and can be used for high-selectivity catalytic synthesis of the sulfur sulfone compounds, and the micro catalyst can make a yield higher, wherein the yield can reach 90% or more; and the photocatalyst and substrate raw materials used in the method are simple and easy to obtain, have low costs and can be produced on a large scale, and the method has very good application prospects.
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Paragraph 0054-0055
(2019/05/15)
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- Switchable Synthesis of Aryl Sulfones and Sulfoxides through Solvent-Promoted Oxidation of Sulfides with O2/Air
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A practical and switchable method for the synthesis of aryl sulfones and sulfoxides via sulfide oxidation was developed. The chemoselectivities of products were simply controlled by reaction temperature using O2/air as the terminal oxidant and oxygen source. The broad substrate scope, easy realization of gram-scale production, and the simplification of a sulfide oxidation system render the strategy attractive and valuable.
- Cheng, Zhen,Sun, Pengchao,Tang, Ailing,Jin, Weiwei,Liu, Chenjiang
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supporting information
p. 8925 - 8929
(2019/11/14)
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- Symmetrical sulfur-containing wet processing type blue organic electroluminescent material as well as preparation method and application thereof
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The invention provides a series of sulfone-containing symmetrical wet process type blue organic electroluminescent materials, which contain sulfones, substituted carbazoles, fluorenes, triphenylamines and derivatives thereof. By a symmetrical design, the electron transmission balance is adjusted; the solubility of molecules is increased by increasing a branched chain of an alkyl chain, wet processing is facilitated and the production cost is reduced. The series of electroluminescent materials relate to the field of electroluminescence, can emit blue and dark blue fluorescence, and can be applied to the fields of OLED (Organic Light Emitting Diode) lighting and OLED display. The material has a strong electron acceptor and a weaker electron donor, a large conjugated structure and a twisted and partially rigid planar structure, the intermolecular force is suppressed, the stability of a device is improved, and high level fluorescence quantum efficiency and blue light material are obtained.
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Paragraph 0047; 0052; 0059; 0060
(2019/10/01)
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- NEW CYCLOADDUCT PRECURSORS OF DIHALODIPHENYLSULFONES AND PREPARATIONS THEREOF
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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'dihalodiphenylsulfones of formula (III) wherein X is as defined above.
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Page/Page column 18
(2019/02/25)
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- Organic monomolecular white light material, preparation method thereof and OLED device
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The invention provides an organic monomolecular white light material, a preparation method of the organic monomolecular white light material and an OLED device. The organic monomolecular white light material disclosed by the invention has room temperature phosphorescence emission properties in a solid state, and can capture triplet excitons to achieve high-efficiency light emission, and the organic monomolecular white light material also has higher thermal decomposition temperature and glass transition temperature, is simple in synthesis method and purification process, mild in reaction conditions and high in yield, and can regulate the thermal properties, luminous efficiency, white color purity and the like of a final product through connecting different aromatic fused ring groups or aromatic heterocyclic groups. The OLED device disclosed by the invention uses the organic monomolecular white light material as a light-emitting layer, and the light-emitting layer of the organic monomolecular white light material is high in brightness and good in stability, so that both the luminous efficiency and the service life of the OLED device can meet practical requirements.
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Paragraph 0086; 0087; 0088; 0089
(2018/08/04)
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- Novel organic semiconductor compound and organic light emitting device using the same
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The present invention relates to a novel organic semiconductor compound, and an organic electroluminescent device using the same. More particularly, the organic semiconductor compound according to the present invention is an azasiline derivative with a rigid structure having an electron doner and an electron acceptor in the molecule, and can embody excellent oxidation stability and light emitting characteristics. The organic electroluminescent device using the same has a high purity blue color having high quantum efficiency. The organic semiconductor compound is represented by chemical formula 1.
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Paragraph 0189-0190; 0195-0197
(2016/10/10)
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- DELAYED FLUORESCENCE COMPOUND, AND ORGANIC LIGHT EMITTING DIODE AND DISPLAY DEVICE USING THE SAME
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Discussed is a delayed fluorescence compound including a first electron donor moiety of indolo-[3,2,1-j,k]carbazole; a second electron donor moiety selected from indolo-[3,2,1-j,k]carbazole, carbazole or triphenylamine; and an electron acceptor moiety selected from dibenzothiophene sulfone or diphenyl sulfone, wherein the first and second electron donor moieties are combined to the electron acceptor moiety, and the electron acceptor moiety is combined to a first position or a para-position of the first electron donor moiety.
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Paragraph 0090; 0091; 0092; 0093; 0166-0169
(2016/10/09)
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- Non-conjugated water/alcohol soluble polymers with different oxidation states of sulfide as cathode interlayers for high-performance polymer solar cells
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A series of non-conjugated water/alcohol soluble copolymers containing diphenyl sulfide, diphenyl sulfoxide or diphenyl sulfone in the main chain were synthesized. The surfactant-like functionalities in side chains endow the polymers with outstanding solubility in highly polar solvents and excellent electron extraction abilities, while the limited conjugation length of main chains renders the polymers weak optical absorption. These unique characteristics make the polymers excellent cathode interfacial layers, which contribute to highly efficient polymer solar cells (PSCs) with power conversion efficiencies of 8-9%. More importantly, some of them can yield highly efficient PSCs in a relative large interlayer thickness range of 2-20 nm. The results suggest that these polymers are promising candidates for use as cathode interfacial layers in single-junction PSCs and as recombination layers in multi-junction PSCs.
- Liu, Xi,Xu, Rongguo,Duan, Chunhui,Huang, Fei,Cao, Yong
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supporting information
p. 4288 - 4295
(2016/06/01)
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- Thermally activated delayed fluorescence materials based on 3,6-di-tert-butyl-9-((phenylsulfonyl)phenyl)-9H-carbazoles
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A series of bipolar materials for thermally activated delayed fluorescence based on 3,6-di-tert-butyl-9-((phenylsulfonyl)phenyl)-9H-carbazoles, is synthesized by Ulmann coupling reactions. In these materials, the 3,6-di-tert-butylcarbazole group is linked at the 3-, 4- position or 3′-, 4′- position of diphenyl sulfone. The effects of the conjugation connectivity on the electronic, photophysical and electrochemical properties of these materials, are studied by extensive UV-vis, fluorescence spectroscopic measurements, cyclic voltammetry and theoretical calculations as well as X-ray crystallographic analysis. The energy gap between singlet and triplet in these materials is tuned from 0.39 eV to 0.22 eV by manipulation of conjugation of the electron donor units.
- Huang, Bin,Qi, Qi,Jiang, Wei,Tang, Jinan,Liu, Yuanyuan,Fan, Wenjuan,Yin, Zhihui,Shi, Fachen,Ban, Xinxin,Xu, Huange,Sun, Yueming
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p. 135 - 144
(2014/07/21)
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- Synthesis of symmetrical diaryl sulfone by homocoupling of sodium arylsulfinate
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An efficient practical homocoupling reaction of sodium arylsulfinate promoted by Cu(II) is reported whereby symmetrical diaryl sulfone derivatives are obtained with high selectivity and reactivity by intermolecular cross-coupling. This homocoupling reacti
- Peng, Yao
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p. 265 - 268
(2014/06/09)
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- The synthesis of diarylsulfones with simple arenes and K2S2O8 through double C-S bond formation
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An unprecedented double C-S bond formation method has been developed to prepare both symmetric and unsymmetric diarylsulfones with simple arenes in a single step. This represents the first example that K2S2O8 can be employed as a highly effective sulfonating agent to synthesize diarylsulfones. The reaction demonstrates excellent reactivity, good functional group tolerance and high yields.
- Yang, Yiqing,Chen, Zhang,Rao, Yu
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supporting information
p. 15037 - 15040
(2014/12/11)
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- Carbazole/sulfone hybrid D-π-A-structured bipolar fluorophores for high-efficiency blue-violet electroluminescence
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Based on a D-π-A structural strategy incorporating carbazole as a mild electron-donor and sulfone as an electron-acceptor with a π-conjugation- breaking feature, two novel blue-violet emitting materials (CzS1 and CzS2) were successfully designed and synthesized. The two compounds exhibit high-efficiency fluorescent emissions of intramolecular charge-transfer transition type, with impressively high quantum yields in both solution and film states. CIE y below 0.06 and excellent current/power efficiencies up to 1.89 cd A-1/1.58 lm W-1 were achieved with their corresponding nondoped devices. These performances currently represent the best results for OLEDs with CIEy 0.06. Moreover, single-carrier devices were also fabricated to demonstrate the bipolar characteristics as well as to understand the different electroluminescence performance of the two fluorophores.
- Ye, Jun,Chen, Zhan,Fung, Man-Keung,Zheng, Caijun,Ou, Xuemei,Zhang, Xiaohong,Yuan, Yi,Lee, Chun-Sing
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p. 2630 - 2637
(2013/07/26)
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- Oxidation kinetics of some sulfoxides with N,N-dibromobenzene sulfonamide
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The kinetics of oxidation of some sulfoxides with dibromamine-B yielding sulfones was investigated in presence of HgII, and the rate equation, kobs = k3K2K′h[S]/[RNH 2] + K′h was found to be valid. The reaction involves two distinct pathways namely initial fast step and a subsequent slow step. The chloride ions have no effect on the reactivity of sulfoxides. Sulfoxides containing electron-attracting substituents retard the reactivity while those containing electron-releasing constituents accelerate the rate of oxidation. Exner plot confirms the operation of same mechanism in all the sulfoxides studied. Electrophilic addition of Br+ to sulfur atom results in an electron-deficient sulfonium centre which decomposes in a slow rate-limiting step. The rate coefficients are treated in terms of multiparametric extensions of the Hammett equation to have more insight into the mechanistic aspects.
- Meenakshisundaram, Subbiah,Amutha
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p. 679 - 682
(2008/09/18)
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- Os(VIII) - Catalysis on the oxidation of some diaryl sulphoxides with bromamine-B in alkaline medium
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The effect of substituents reveals the electronic character of Os(VIII)- catalysed N-bromobenzene sulphonamide (bromamine-B) oxidation of some diaryl sulphoxides to sulphones in a strongly alkaline (pH-11.5) t-butanol-water (1:1 v/v) medium and the conversion appears to be nucleophilic for bromamine-B (BAB). High dielectric constant of the medium favours the reactivity. The kinetic studies reveal that electron-withdrawing groups enhance the reactivity while electron-releasing ones inhibit the rate. It appears that the anion RNBr is the reactive species of bromamine-B. The possibility of the formation of Os(VI)-BAB complex causing a retarding effect on the pseudo-first-order rate coefficients is discussed. Contrary to expectations there is a marked depression in the catalytic activity of Os(VIII) in the presence of other transition metals and pyridine bases such as 2, 2′-bipyridyl and 1,10-phenanthroline. The probable reaction mechanisms are discussed on the basis of above results.
- Meenakshisundaram, Subbiah,Markkandan, Ramakrishnan
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- Polymer electrolyte and process for producing the same
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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.
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- Mechanism of oxygenation of aryl methyl and diaryl sulphoxides by peroxomonophosphoric acid
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The kinetics of oxygenation of the title sulphoxides by peroxomonophosphoric acid in aqueous acetic acid follows an overall second-order kinetics, first-order in each reactant. An analysis of the influence of [H+] reveals that H3PO5 is the active species in the oxidation. The structure - reactivity studies with different substituents on the phenyl ring give evidence for the formation of an electron deficient sulphonium ion intermediate as the correlation between log k2 and σ gives a negative ρ value (ρ=-0.47±0.09, r=0.988, s=0.03 at 35°C for aryl methyl sulphoxides and ρ=-0.54±0.11, r=0.983, s=0.07 at 35°C for diaryl sulphoxides). It is proposed that the mechanism involves the nucleophilic attack of the sulphoxide sulphur on the peroxo-oxygen of H3PO5 in the rate-limiting step.
- Suthakaran,Rajagopal,Srinivasan
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p. 1369 - 1374
(2007/10/03)
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- Catalysis of the oxone oxidation of some sulphoxides by Ru(III)
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The kinetics of oxidation of some sulphoxides with oxone in the presence of Ru(III) has been described. The catalytic activity of Ru(III) has been demonstrated with several diaryl, dialkyl and alkyl aryl sulphoxides, all of which are found to undergo oxidation under homogenous conditions. Homolytic fission of the peroxide bond is ruled out. The reaction exhibits first-order dependence on the concentration of Ru(III) is observed. Reactions have small substituent effects with ρ = -0.3. The rates increase substantially with increasing water content in aqueous acetic acid. The rate data are consistent with the mechanism involving electron transfer from electrophilic perhydroxyl oxygen of oxone to sulphoxide. The rate coefficients are treated in terms of multiparameter extensions of the Hammett equation to have more insight into the mechanistic aspects.
- Meenakshisundaram, Subbiah,Sathiyendiran, V.
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p. 1118 - 1133
(2007/10/03)
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- Differences in the Course of Reactions of N,N-Dichloroamides of Carboxylic and Sulfonic Acids with Diaryl Sulfoxides
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N,N-Dichloroamides of carboxylic acids are donors of oxygen in the reaction with diaryl sulfoxides that results in the formation of diaryl sulfones and the corresponding nitriles (oxidation of sulfoxides).N,N-Dichloroamides of sulfonic acids in the reaction with the same sulfoxides form N-arylsulfonyl-S,S-diarylsulfoxyimines (imination of sulfoxides).Based on the results of the MNDO calculations, probable intermediates responsible for realizing of a certain reaction pathway are suggested.
- Pigin, O. V.,Krasnov, V. L.,Groshev, Yu. G.,Bel'skii, V. K.,Bodrikov, I. V.
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p. 1520 - 1525
(2007/10/03)
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- Oxidation of some Disubstituted Diphenyl Sulphoxides with Sodium N-Bromobenzene Sulphonamide in Presence of Mercury(II). A Kinetic and Mechanistic Study
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Kinetics of bromamine-B (BAB) oxidation of some p- and p'-disubstituted sulphoxides, to give the corresponding sulphones, have been studied in aqueous acetic acid medium.A first order dependence on the concentration of each reactant was observed.Rate data showed an inverse dependence on and a fractional order in +>.The reactions are little affected by the addition of HgII, ruling out the catalytic role.A negative ρ value suggests the sulphur becoming electron-dificient in the transition state.The rate-limiting step involves the interaction of the substrate and +> species.
- Mangalam, G.,Sundaram, Subbiah Meenakshi
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p. 819 - 821
(2007/10/02)
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- Kinetics and mechanism of oxidation of dimethyl, methyl phenyl and diaryl sulphoxides by N-bromocaprolactam
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The oxidation of dimethyl (DMSO) and methyl phenyl (MPSO) sulphoxides by N-bromocaprolactam (NBC) follows zero order kinetics in , but that of diphenyl sulphoxide (DPSO) is first order in .HClO4 accelerates the rate of all the oxidation reactions.However, added caprolactam retards the oxidation of only DPSO.
- Srinivasan, C.,Jegatheesan, P. Pandarakutty
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p. 250 - 252
(2007/10/02)
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- NMR Study of Substituent Effects in 4-Substituted and 4,4'-Disubstituted Diphenyl Sulphoxides and Sulphones
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The proton and carbon NMR spectra of nine 4-X-diphenyl sulphoxides, seven 4-X-4'-NO2-diphenyl sulphoxides, eight 4,4'-X2-diphenyl sulphoxides, eight 4-X-diphenyl sulphones, seven 4-X-4'-NO2-diphenyl sulphones and eight 4,4'-X2-diphenyl sulphones have been obtained.Correlation of the 13C chemical shifts with the appropriate substituent chemical shifts (SCS) for monosubstituted benzenes (Lynch plots) does not show the enhancement of substituent effect at C-1 (para to the substituent) that was a feature of the corresponding sulphides studied earlier.Dual substituent parameter (DSP) correlations of the 13C chemical shifts with ?I/?R0 are excellent for carbons meta (C-2,6) and para (C-1) to the substituent.The trends for the series sulphides, sulphoxides, sulphones, where a decreasing response to the change of substituent is the general observation, are discussed.Changes of molecular conformation may also influence the transmission of electronic effects to the ring not carrying the variable substituent X. KEY WORDS 1H NMR 13C NMR Diphenyl sulpoxides Diphenyl sulphones Substituent effects
- Chandrasekaran, R.,Perumal, S.,Wilson, D. A.
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p. 360 - 367
(2007/10/02)
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- SYNTHESIS OF CARBOMETHOXYDIPHENYL SULFONES. MASS AND PROTON-NMR SPECTRAL STUDIES
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Four carbomethoxydiphenyl sulfone compounds are formed in the reaction of 4,4'-dibromo (I) and 4,4'-diiododiphenyl sulfone (II) with n-butyllithium in tetrahydrofuran at -60 deg C.Their mass and proton-nuclear magnetic resonance spectra are discussed.
- Brinon, M.C.,Bertorello, M.M. de,Bertorello, H.E.,Luna, L.
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- Substituent effects in cooxidation: Cr(VI) - oxalic acid - sulfoxides systems
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The kinetics of cooxidation of several substituted phenyl methyl sulfoxides and oxalic acid with Cr(VI) have been carried out in the presence of perchloric acid.The reaction is first order each in sulfoxide, oxalic acid, Cr(VI), and H1+.The products of oxidation are sulfones and carbon dioxide.Electron-releasing groups in the phenyl ring accelerate the rate while electron-withdrawing groups retard it.The Hammett correlation yields a reaction constant of -0.927 +/- 0.08 (r = 0.994) at 313 K.Addition of aluminum nitrate prevents the occurence of cooxidation.Based on the kinetic information a suitable mechanism has been proposed.Diaryl sulfoxides behave in an analogous manner in the cooxidation.
- Srinivasan, C.,Jegatheesan, P. Pandarakutty,Rajagopal, S.,Arumugam, N.
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p. 2421 - 2424
(2007/10/02)
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- Mechanism of Oxidation of Aryl Methyl Sulphoxides and Diaryl Sulphoxides by Potassium Bromate
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The oxidation of aryl methyl and diaryl sulphoxides in aqueous acetic acid at constant and ionic strength is first order each in and .An excellent correlation exists between logk2 and the Hammett ? constants (ρ=-2.05, r=0.997, s=0.05, confidence limit on ρ=+/-0.10 in 50percent aq acetic acid (v/v) at 35 deg for aryl methyl sulphoxides and ρ=-1.82, r=0.992, s=0.12, confidence limit on ρ=+/-0.32 in 75percent aq acetic acid (v/v) at 35 deg for diaryl sulphoxides).The high negative ρ-value in the two series indicates considerable charge development in the transition state.
- Srinivasan, C.,Jegatheesan, P. Pandarakutty,Arumugam, N.
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p. 678 - 680
(2007/10/02)
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- Sulfosilylation of Aromatic Hydrocarbons by Trimethylsilyl Chlorosulfonate
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Aromatic hydrocarbons 2 ,6 ,8 ,9 ,13 ,16 ,18 ,19 ,22 react with trimethylsilyl chlorosulfonate (1) to give trimethylsilyl arenesulfonates 5, 7, 11, 12, 15, 23 or sulfonic acids 17, 20, 21.If trimethylsilyl sulfonates are obtained, working up of the sulfonation mixtures is possible by distillation.By hydrohalogenolysis of trimethylsilyl sulfonates 5 at 0-5 deg C anhydrous sulfonic acids 3 result.The pathways to diphenylsulfone (25a) in the reaction of benzene (2a) with 1 were investigated.In this connection we succeeded in synthesizing benzenepyrosulfonic acid (28) and trimethylsilyl benzenepyrosulfonate (29).
- Hofmann, Karin,Simchen, Gerhard
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p. 282 - 297
(2007/10/02)
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- Kinetics and Mechanism of Oxidation of Diaryl Sulphoxides by Cr(VI)
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The kinetics of oxidation of a few diaryl sulphoxides by Cr(VI) in 75percent aqueous acetic acid has been studied.The reaction follows second-order kinetics, first-order each in sulphoxide and Cr(VI).A mechanism analogous to the one proposed for the oxidation of aryl methyl sulphoxides has been suggested.
- Srinivasan, C.,Venkatasamy, R.,Rajagopal, S.
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p. 505 - 506
(2007/10/02)
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