Showing papers on "Benzophenone published in 2014"
TL;DR: Organic light-emitting diodes with these benzophenone derivatives doped in the emissive layer can generate electroluminescence ranging from blue to orange-red and white, with maximum external quantum efficiencies of up to 14.3%.
Abstract: Butterfly-shaped luminescent benzophenone derivatives with small energy gaps between their singlet and triplet excited states are used to achieve efficient full-color delayed fluorescence. Organic light-emitting diodes (OLEDs) with these benzophenone derivatives doped in the emissive layer can generate electroluminescence ranging from blue to orange-red and white, with maximum external quantum efficiencies of up to 14.3%. Triplet excitons are efficiently harvested through delayed fluorescence channels.
468 citations
TL;DR: The present protocol serves as an efficient method for the direct extension of carbon skeletons for the synthesis of structurally complex natural products and pharmaceuticals.
Abstract: The direct alkenylation of C(sp3)–H bonds was achieved by employing benzophenone and 1,2-bis(phenylsulfonyl)ethylene under photo-irradiation conditions. This simple metal-free reaction enables the substitution of heteroatom-substituted methine, methylene and aliphatic C(sp3)–H bonds by (E)-sulfonylalkene units in a highly chemoselective manner. The derived sulfonylalkenes were further converted in a single step to the prenyl derivatives via a second photo-induced radical substitution and to the pyrrole derivatives via cyclization and aromatization steps. The present protocol thus serves as an efficient method for the direct extension of carbon skeletons for the synthesis of structurally complex natural products and pharmaceuticals.
89 citations
TL;DR: In vitro tests in several cell models showed that 2 and its 3-C-monoglucosylated derivative were marginally effective in increasing glucose uptake and α-glucosidase inhibitory activity against an enzyme mixture extracted from rat intestinal acetone powder.
Abstract: An enriched fraction of an aqueous extract prepared from the aerial parts of Cyclopia genistoides Vent. yielded a new benzophenone di-C,O-glucoside, 3-C-β-d-glucopyranosyl-4-O-β-d-glucopyranosyliriflophenone (1), together with small quantities of a known benzophenone C-glucoside, 3-C-β-d-glucopyranosylmaclurin (2). The isolated compounds showed α-glucosidase inhibitory activity against an enzyme mixture extracted from rat intestinal acetone powder. Compound 2 exhibited significantly (p < 0.05) higher inhibitory activity (54%) than 1 (43%) at 200 μM. In vitro tests in several cell models showed that 1 and its 3-C-monoglucosylated derivative (3-C-β-d-glucopyranosyliriflophenone) were marginally effective (p ≥ 0.05) in increasing glucose uptake.
51 citations
Patent•
09 Jul 2014
46 citations
TL;DR: Molecular structures of complexes (2, 4-7) show that κ(N,N') bonding between a DippForm and samarium atom exists in all compounds, but in 2, Dipp form also bridges K and Sm by 1κ(N):2κ( N') bonding and two 2,6-diisopropylphenyl groups are η(6)-bonded to potassium.
Abstract: The preparation of a new heterobimetallic samarium(II) formamidinate complex and selected reactions of samarium(II) complexes and one samarium(III) formamidinate complex with benzophenone or CS2 are discussed. Treatment of the tris(formamidinato)samarium(III) complex [Sm(DippForm)3] 1 (DippForm = N,N′-bis(2,6-diisopropylphenyl)formamidinate, (CH(NC6H3-iPr2-2,6)2) with potassium graphite in toluene yielded the dark brown heterobimetallic formamidinatosamarium(II)/potassium complex [KSm(DippForm)3]n 2. Divalent 2, a Lewis base solvent free homoleptic species, differs significantly from the related heteroleptic formamidinatosamarium(II) complex [Sm(DippForm)2(thf)2] 3 with respect to its constitution, structure, and reactivity toward benzophenone. While 2 reacts giving complex 1, the reaction of 3 with benzophenone generates the highly unusual [Sm(DippForm)2(thf){μ-OC(Ph)═(C6H5)C(Ph)2O}Sm(DippForm)2] (C6H5 = 1,4-cyclohexadiene-3-yl-6-ylidene) 4. The formation of 4 highlights a rare C–C coupling between a car...
45 citations
TL;DR: In this article, the potential of UV irradiation assisted generation of free radicals on the surface benzophenone units to graft a variety of polymer chains on the PEEK surface was explored by using different monomers and polymers.
Abstract: Polyether ether ketone (PEEK) is a thermoplastic polymer of high technological relevance and is composed of repeating phenyl ether and benzophenone units. In the present work we will demonstrate the potential of UV irradiation assisted generation of free radicals on the surface benzophenone units to graft a variety of polymer chains on the PEEK surface. Both “grafting-to” and “grafting-from” approaches were explored by using different monomers and polymers. Styrene, butyl acrylate (BA), vinyl phosphonic acid (VPA), acrylic acid (AA), polyacrylic acid (PAA) and monomethoxy terminated oligo (ethylene glycol) methacrylate (MeOEGMA) were successfully utilized for this purpose. The functionalized membranes were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier-transformed Infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and contact angle (CA) goniometry. PAA and PVPA functionalized PEEK surfaces exhibited pH responsive wettability behavior. PAA functionalized PEEK surfaces were further modified with lysine, which led to the controlled surface wettability over a broader pH range as compared to the simple PAA functionalized surface. The grafting with polyMeOEGMA rendered PEEK surface with nonfouling properties against bacterial growth. Employing this highly economical and simple method, the surface properties of PEEK can be modulated and tuned according to a specific application.
40 citations
TL;DR: Polymeric benzophenone photoinitiator (PEG-BP) was synthesized basing on polyethylene glycol, succinic anhydride, 4-hydroxybenzophenone and epichlorohydrin this article.
37 citations
TL;DR: The compound 10h with a methyl and fluoro groups at benzophenone moiety and methoxy group at phenyl ring was in a leading position to exhibit the promising antiproliferative effect through translational VEGF-A inhibition.
35 citations
TL;DR: It is found that the triplet formation can be described almost as a direct process in preparing T1, the lowest reacting triplet state, from the S1 state after S2 → S1 internal conversion.
Abstract: Benzophenone is a prototype molecule for photochemistry in the triplet state through its high triplet yield and reactivity. We have investigated its dynamics of triplet formation under the isolated gas phase conditions via femtosecond and nanosecond time resolved photoelectron spectroscopy. This represents the complete evolution from the excitation in S2 to the final decay of T1 to the ground state S0. We have found that the triplet formation can be described almost as a direct process in preparing T1, the lowest reacting triplet state, from the S1 state after S2 → S1 internal conversion. The molecule was also deposited by a pick-up technique on cold argon clusters providing a soft relaxation medium without evaporation of the molecule and the mechanism was identical. This cluster technique is a model for medium influenced electronic relaxation and provides a continuous transition from the isolated gas phase to the relaxation dynamics in solution.
34 citations
TL;DR: Kinetic studies revealed two possible expressions for the rate of product formation, depending on which catalyst resting state was present, and either 1a, 5a, or both 1a and 5a could be observed as resting states of the catalytic cycle,depending on the initial [PhMeSiH2]:[benzophenone] ratio.
Abstract: The electrophilic η3-H2SiRR′ σ-complexes [PhBPPh3]RuH(η3-H2SiRR′) (RR′ = MePh, 1a; Ph2, 1b; [PhBPPh3]− = [PhB(CH2PPh2)3]−) are efficient catalysts (0.01–2.5 mol % loading) for the hydrosilation of ketones with PhMeSiH2, Ph2SiH2, or EtMe2SiH. An alkoxy complex [PhBPPh3]Ru–OCHPh2 (4b) was observed (by 31P{1H} NMR spectroscopy) as the catalyst resting state during hydrosilation of benzophenone with EtMe2SiH. A different catalyst resting state was observed for reactions using PhMeSiH2 or Ph2SiH2, and was identified as a silane σ-complex [PhBPPh3]RuH[η2-H–SiRR′(OCHPh2)] (RR′ = MePh, 5a; Ph2, 5b) using variable temperature multinuclear NMR spectroscopy (−80 to 20 °C). The hydrosilation of benzophenone with PhMeSiH2 and 1a was examined by 1H NMR spectroscopy at −18 °C (in CD2Cl2), and this revealed that either 1a, 5a, or both 1a and 5a could be observed as resting states of the catalytic cycle, depending on the initial [PhMeSiH2]:[benzophenone] ratio. Kinetic studies revealed two possible expressions for the rat...
34 citations
TL;DR: The UV absorption, phosphorescence and phosphorescence‐excitation spectra of benzophenone (BP) derivatives used as organic UV absorbers have been observed in rigid solutions at 77 K and the possible mechanism of the observed phosphorescence enhancement is discussed.
Abstract: The UV absorption, phosphorescence and phosphorescence-excitation spectra of benzophenone (BP) derivatives used as organic UV absorbers have been observed in rigid solutions at 77 K. The triplet-triplet absorption spectra have been observed in acetonitrile at room temperature. The BP derivatives studied are 2,2',4,4'-tetrahydroxybenzophenone (BP-2), 2-hydroxy-4-methoxybenzophenone (BP-3), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (BP-6), 5-chloro-2-hydroxybenzophenone (BP-7) and 2-hydroxy-4-n-octyloxybenzophenone (BP-12). The energy levels and lifetimes of the lowest excited triplet (T1 ) states of these BP derivatives were determined from the first peak of phosphorescence. The time-resolved near-IR emission spectrum of singlet oxygen generated by photosensitization with BP-7 was observed in acetonitrile at room temperature. BP-2, BP-3, BP-6 and BP-12 show photoinduced phosphorescence enhancement in ethanol at 77 K. The possible mechanism of the observed phosphorescence enhancement is discussed. The T1 states of 2-hydroxy-5-methylbenzophenone, 4-methoxybenzophenone and 2,4'-dimethoxybenzophenone have been studied for comparison.
TL;DR: This work successfully substituted the right-hand imidazole ring with a branched alkyl chain at the 5-position in 1 with a simpler 2-pyridyl structure by converting the left-hand ring from a phenyl to a benzophenone structure without decreasing the potency.
Abstract: A new benzophenone–diketopiperazine-type potent antimicrotubule agent was developed by modifying the structure of the clinical candidate plinabulin (1). Although the right-hand imidazole ring with a branched alkyl chain at the 5-position in 1 was critical for the potency of the antimicrotubule activity, we successfully substituted this moiety with a simpler 2-pyridyl structure by converting the left-hand ring from a phenyl to a benzophenone structure without decreasing the potency. The resultant compound 6b (KPU-300) exhibited a potent cytotoxicity, with an IC50 value of 7.0 nM against HT-29 cells, by strongly binding to tubulin (Kd = 1.3 μM) and inducing microtubule depolymerization.
TL;DR: In this paper, a monomeric photoinitiator with a side-chain benzophenone group was synthesized from tert-butyl α-bromo methacrylate (TBBr) and 4-hyroxybenzophenone.
Abstract: A novel monomeric photoinitiator, tert-butyl 2-((4-benzoylphenoxy)methyl)acrylate (1), with a side-chain benzophenone (BP) group was synthesized from tert-butyl α-bromo methacrylate (TBBr) and 4-hyroxybenzophenone. It was thermally homo- and copolymerized with a coinitiator, N,N-dimethylaminoethyl methacrylate (DMAEM), using free radical polymerization to give the corresponding polymeric photoinitiators (poly-1 and poly(1-co-DMAEM)). The polymeric photoinitiators showed similar UV absorption spectra to 1, which were red-shifted compared to BP. Photophysical studies such as phosphorescence and laser flash photolysis in addition to photopolymerization of methacrylates were performed. The photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) and 1,6-hexanedioldiacrylate (HDDA) initiated by 1, poly-1, poly(1-co-DMAEM) and BP were studied by photo-DSC. The polymeric initiator (poly-1) was found to have higher efficiency than BP and monomeric initiatior 1.
TL;DR: In this paper, a one-step preparation of α-sulfonylated cyclic ethers has been achieved via the intermolecular sulfonylation of ethereal C H bonds.
TL;DR: The synthesis, full characterization, photoreduction properties, and catalytic activity for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction of a copper(II)-DMEDA (N,N'-dimethylethylendiamine) complex is reported.
Abstract: The synthesis, full characterization, photoreduction properties, and catalytic activity for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction of a copper(II)-DMEDA (N,N′-dimethylethylendiamine) complex is reported. Spectroscopic studies (UV/Vis, EPR) demonstrated that under daylight illumination highly effective copper(II) to copper(I) reduction occurs in this complex. These findings are in agreement with a high photoreduction quantum yield value of 0.22 in MeOH, and a value approaching unity as determined in THF. The reduction process, which can also be conducted by irradiation at 365 nm by using a standard TLC (thin layer chromatography) lamp, is ascribed to a highly efficient photoinduced electron transfer (PET) process mediated by the benzophenone photosensitizer present in the carboxylate counterion. Having deaerated the reaction mixture, the photogenerated copper(I) species proved to be highly active for the CuAAC reaction, demonstrated by reactions conducted with low catalyst loading (0.5 mol %) on a range of clickable protected and non-protected mono- and disaccharides. Once initiated, the reaction can be stopped at any time on introducing air into the reaction medium. Deoxygenation followed by irradiation restores the activity, making the copper(II)-DMEDA complex a switchable catalyst of practical value.
TL;DR: In this article, the electronic preference for the formation of a ketyl radical complex or a coordination complex has been investigated computationally, and the reaction between 1 and imines was allowed to react with 1, generating new complexes that bind the thione to the Co rather than undergoing singleelectron transfer.
TL;DR: The first uranium(III) charge separated ketyl radical complex, Tp*2U(OC·Ph2), has been isolated and characterized by infrared, (1)H NMR, and electronic absorption spectroscopies, along with X-ray crystallography.
Abstract: The first uranium(III) charge separated ketyl radical complex, Tp*2U(OC·Ph2), has been isolated and characterized by infrared, 1H NMR, and electronic absorption spectroscopies, along with X-ray crystallography. Tp*2U(OC·Ph2) is a potent two-electron reductant towards N3Mes (Mes = 2,4,6-trimethylphenyl) and (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO), with reducing equivalents derived from the metal centre and the redox-active benzophenone.
TL;DR: A Ni(II) glycine/Schiff base complex containing (S)-o-[N-(N-benzylprolyl)amino]benzophenone as an auxiliary chiral moiety was deprotonated using electrochemically generated azobenzene radical anion.
TL;DR: In this article, the self developable performance of benzophenone doped polydimethylsiloxane (PDMS) using laser lithography was discussed, which indicated that addition of 3.0 ¼ w.t.% benophenone in PDMS enhance self development sensitivity of PDMS.
TL;DR: The results indicate that specific interactions of the sorbate and the presence of domains in the sorbent influence the magnitude and selectivity of sorption.
Abstract: Specific functional-group or domain interactions of fully deuterium-exchanged, carbonyl-(13)C-labeled benzophenone and different types of natural organic matter (NOM) were investigated through two-dimensional (1)H-(13)C heteronuclear correlation NMR spectroscopy. The sorbents included Beulah-Zap lignite, type II kerogen (IL-6), Pahokee peat, Amherst humic acid, and a polystyrene-poly(vinylmethyl ether) (PS-PVME) blend. PS-PVME consists of PS and PVME chains that are mixed on a scale of <5 nm. The NOM sorbents all consist predominantly of a mixed aromatic-alkyl or aromatic-O-alkyl matrix that is homogeneous on the 3 nm scale, as evidenced by fast equilibration of aromatic and alkyl (1)H magnetization. In addition, Beulah lignite and IL-6 kerogen exhibit small fractions of distinct polymethylene (CH2)n domains, and Pahokee peat contains significant fractions of polar and nonpolar alkyl domains. Benzophenone-((13)C═O)-d10 shows proximity to both aromatic rings and alkyl segments in all samples but preferentially interacts with aromatic rings in PS-PVME and Beulah lignite, possibly due to π-π electron donor-acceptor interactions. The data for IL-6 kerogen are also compatible with preferential location of benzophenone near the alkyl-substituted edges of aromatic rings, while in Pahokee peat, clear signatures of benzophenone affinity to both aromatic-rich and nonpolar alkyl domains have been detected. Amherst humic acid shows evidence of some affinity to polar alkyl segments but which is weaker than that to aromatic rings. Our results indicate that specific interactions of the sorbate and the presence of domains in the sorbent influence the magnitude and selectivity of sorption.
TL;DR: A series of N-phthaloyltranexamic acid ammonium salt derivatives based on benzophenone, thioxanthen, and naphtha chromophores as novel photocaged bases were synthesized and characterized as discussed by the authors.
TL;DR: In this paper, a well-dispersed Co-Mn catalyst was used for the selective synthesis of benzophenone by liquid phase oxidation of diphenylmethane under various reaction conditions.
Abstract: A well-dispersed Co–Mn catalyst immobilized on calcined Cow bone was synthesized and used, for the first time for the selective synthesis of benzophenone by liquid phase oxidation of diphenylmethane under various reaction conditions. The catalyst was characterized using techniques such as UV–vis, SEM, TEM and BET. The catalyst has shown an excellent activity (87%), selectivity to diphenyl ketone (90%) and stability under solvent free conditions. To investigate the leaching of the metals from the support, results of the original and reusable catalyst was correlated and compared, and the catalytic activity of washed catalyst was also demonstrated. Based on the all catalytic results for this reaction, the new catalyst was found to be a highly active and environmentally friendly solid catalyst and has superior catalytic activity.
TL;DR: It was demonstrated that 2-(3-fluoren-9-ylideneaminooxy)-2-hydroxy-propylamino)-3-methyl-butanoic acid as the most potent compound substantially reduces the heart rate of dogs and potential drug toxicity for some active compounds has been predicted.
Abstract: The syntheses and biological studies of O-oxime ethers having α-amino acid residues as new analogs of IPS-339 have been described. In this synthesis, the reaction of fluorene and/or benzophenone O-oxime with epichlorohydrin or epibromohydrin afforded the corresponding O-oxime ether adducts. The N-alkylation of amino acid with O-oxime ether adducts led to synthesis of new analogs of IPS-339. The products were examined for their cardiovascular property. It was demonstrated that 2-(3-(9H-fluoren-9-ylideneaminooxy)-2-hydroxypropylamino)-3-methyl-butanoic acid as the most potent compound substantially reduces the heart rate of dogs. Compounds were also evaluated for their in vitro antibacterial activity against some Gram-negative and Gram-positive bacteria. The antibacterial screening proved the considerable antibacterial activity against both groups of bacteria. The docking analysis demonstrated the appropriate fitting of 2-(3-(9H-fluoren-9-ylideneaminooxy)-2-hydroxy-propylamino)-3-methyl-butanoic acid in human β2-adrenergic receptor active site. Potential drug toxicity for some active compounds has also been predicted.
TL;DR: It is indicated that benzophenone hydrazone N-acylated thiourea and urea derivatives could be used as potential lead compounds for developing novel acaricides and insecticides.
Abstract: BACKGROUND
Benzophenone hydrazone derivatives are among the most important classes of synthetic insecticides. In an effort to discover new molecules with good insecticidal/acaricidal activities, a series of novel benzophenone hydrazone N-acylated thiourea and urea derivatives was synthesized and bioassayed.
RESULTS
All of these compounds exhibited excellent bioactivities against T. cinnabarinus and B. brassicae, especially towards T. cinnabarinus with LC50 values ranging from 0.305 to 2.036 mmol L-1. Moreover, the acaricidal activities against T. cinnabarinus of compounds 8a–i, 12b–f and 12h were 2.5–5.5-fold that of parent molecule 3 based on the LC50 value.
CONCLUSION
Based on the observed bioactivities, the structure–activity relationship of these analogs was also discussed. Structure–activity relationships provided information that could direct further investigation on structure modification. Our studies indicated that benzophenone hydrazone N-acylated thiourea and urea derivatives could be used as potential lead compounds for developing novel acaricides and insecticides. © 2013 Society of Chemical Industry
TL;DR: The FT-IR and FT-Raman spectra of 3,3'-bis (trifluoromethyl) benzophenone (TFMBP) were recorded and analyzed and comparison of the experimental and theoretical spectra values provides important information about the ability of the computational method to describe the vibrational modes.
TL;DR: In this paper, the sulfonated polyphenylenes containing benzophenone structure (sulfonated Parmax 1200, S-Parmax) were prepared by sulfonation reaction with 30% fuming sulfuric acid.
TL;DR: Simulations of the anti-phase structure (APS) line shape of these spin correlated radical pairs (SCRPs) based on a numerical solution of the Stochastic Liouville Equation with the spin exchange interaction depending exponentially on the distance between radicals are presented and discussed.
Abstract: Radical pairs created by the photoreduction of benzophenone (BP) in sodium dodecyl sulfate (SDS) micelles exhibit strong asymmetry in the line shapes of their time-resolved electron paramagnetic resonance (TREPR) signals. The asymmetry is strongly dependent on the temperature from 16 °C to 66 °C. Simulations of the anti-phase structure (APS) line shape of these spin correlated radical pairs (SCRPs), based on a numerical solution of the Stochastic Liouville Equation with the spin exchange interaction depending exponentially on the distance between radicals, are presented and discussed. The proposed model takes into account the diffusive motion of the radicals along with the motion of the transverse magnetization and accounts satisfactorily and self-consistently for the asymmetry of the observed TREPR signals.
TL;DR: Magnetic field effects on photo-induced electron transfer reaction between benzophenone and 1,4-diazabicyclo [2.2] octane in an ionic liquid (IL) of N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl) amide were studied by a nanosecond laser flash photolysis technique.
Abstract: Magnetic field effects (MFEs) on photoinduced electron transfer reaction between benzophenone (BP) and 1,4-diazabicyclo [2.2.2] octane in an ionic liquid (IL) of N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl) amide were studied by a nanosecond laser flash photolysis technique. The escape yield of the benzophenone radical anion (BP•–) was increased with increasing magnetic field strength (B) of 0 T < B ≤ 0.1 T and almost saturated at 0.1 T < B ≤ 1.7 T. The observed MFEs were explained by the hyperfine coupling mechanism (HFCM) and the relaxation mechanism (RM). The large MFEs indicate the nanometer-scaled cage effects on the diffusion of the radical ion pairs (RIP) generated by the photoinduced electron transfer reaction in TMPA TFSA. The cage lifetime for the RIP was estimated to be 170 ns, which is much longer than that previously reported for the neutral radical pairs (<20 ns) in the same IL. In addition to the large MFEs due to the HFCM and the RM, we also observed the MFE caused by the...
TL;DR: In this article, a novel polymeric photoinitiator, poly(glycidyl benzophenone ether) (PGBE), with a side-chain benzophenones (BP) group was synthesized from poly(epichlorohydrin) and 4-hydroxybenzophenone.
TL;DR: In this article, a nickel-catalyzed method for the crosscoupling of benzophenone hydrazone with aryl bromides is described and the use of a simple Ni(II)/NHC catalyst leads to arylated hydrazones in good or acceptable yields.
Abstract: A nickel-catalyzed method for the cross-coupling of benzophenone hydrazone with aryl bromides is described The use of a simple Ni(II)/NHC catalyst leads to the arylated hydrazones in good or acceptable yields This protocol provides a simple, convenient alternative to the synthesis of arylhydrazines