1080-32-6Relevant articles and documents
2D Ultrafast HMBC 1H,31P: Obtaining mechanistic details on the Michaelis-Arbuzov reaction
Fernández-Valle, María Encarnación,Martínez-álvarez, Roberto,Molero-Vílchez, Dolores,Pardo, Zulay D.,Sáez-Barajas, Elena,Herrera, Antonio
, p. 799 - 805 (2015)
Ultrafast NMR spectroscopy (UF-NMR) can be used to monitor chemical reactions in real time and to provide insights into their mechanisms and the nature of the intermediates formed. Here, we have developed a 2D 1H,31P UF-HMBC method and the corresponding NMR experimental setup to enable the study of a Michaelis-Arbuzov reaction at two different temperatures, 25 and 70 °C. The specific reaction studied was between triethyl phosphite and benzyl bromide to produce diethylbenzyl phosphonate. Our results show that at 70 °C the reaction takes place directly, without the detection of an intermediate by 1H,31P UF-HMBC. In contrast, at 25 °C, using zinc bromide as a catalyst, our results show the formation of benzyltriethoxy phosphonium bromide as an intermediate. The experiments again show the power of UF-NMR in mechanistic studies of reactions involving various phosphorus chemical species.
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Levin et al.
, p. 487 (1973)
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Crystal structures of the apo form and a complex of human LMW-PTP with a phosphonic acid provide new evidence of a secondary site potentially related to the anchorage of natural substrates
Fonseca, Emanuella M.B.,Trivella, Daniela B.B.,Scorsato, Valéria,Dias, Mariana P.,Bazzo, Natália L.,Mandapati, Kishore R.,De Oliveira, Fábio L.,Ferreira-Halder, Carmen V.,Pilli, Ronaldo A.,Miranda, Paulo C.M.L.,Aparicio, Ricardo
, p. 4462 - 4471 (2015)
Low molecular weight protein tyrosine phosphatases (LMW-PTP, EC 3.1.3.48) are a family of single-domain enzymes with molecular weight up to 18 kDa, expressed in different tissues and considered attractive pharmacological targets for cancer chemotherapy. Despite this, few LMW-PTP inhibitors have been described to date, and the structural information on LMW-PTP druggable binding sites is scarce. In this study, a small series of phosphonic acids were designed based on a new crystallographic structure of LMW-PTP complexed with benzylsulfonic acid, determined at 2.1 ?. In silico docking was used as a tool to interpret the structural and enzyme kinetics data, as well as to design new analogs. From the synthesized series, two compounds were found to act as competitive inhibitors, with inhibition constants of 0.124 and 0.047 mM. We also report the 2.4 ? structure of another complex in which LMW-PTP is bound to benzylphosphonic acid, and a structure of apo LMW-PTP determined at 2.3 ? resolution. Although no appreciable conformation changes were observed, in the latter structures, amino acid residues from an expression tag were found bound to a hydrophobic region at the protein surface. This regions is neighbored by positively charged residues, adjacent to the active site pocket, suggesting that this region might be not a mere artefact of crystal contacts but an indication of a possible anchoring region for the natural substrate - which is a phosphorylated protein.
Ivanov,Krokhina
, (1970)
The photoisomerization of: Cis, trans -1,2-dideuterio-1,4-diphenyl-1,3-butadiene in solution. No bicycle-pedal
Saltiel, Jack,Redwood, Christopher E.,Ratheesh Kumar
, p. 2174 - 2179 (2019)
cis,trans-1,2-Dideuterio-1,4-diphenyl-1,3-butadiene (ct-DPBd2) was synthesized and its cis-trans photoisomerization in cyclohexane-d12 (C6D12) at room temperature was monitored by 1H NMR spectroscopy. The results reveal formation of only trans,trans-1,2-dideuterio-1,4-diphenyl-1,3-butadiene (tt-DPBd2). The failure to detect formation of trans,cis-1,2-dideuterio-1,4-diphenyl-1,3-butadiene (tc-DPBd2) eliminates the possibility that an identity bicycle pedal process contributes to inefficiency in the cis-trans photoisomerization of cis,trans-1,4-diphenyl-1,3-butadiene (ct-DPB).
Synthesis, UV/vis spectra and electrochemical characterisation of arylthio and styryl substituted ferrocenes
Sorensen, Thomas J.,Nielsen, Merete F.
, p. 610 - 618 (2011)
Two series of substituted ferrocenes were synthesised using either the Horner-Wadswor th-Emmons reaction or monolithiation of ferrocene. The series consist of arylthio- and styryl-ferrocenes with different substituents in the para position of the aryl rings of the systems. The electronic communication was investigated by comparing the substituent effects in absorption spectroscopy and in cyclic voltammetry. A small substituent effect was found in the electronic transitions of the styryl substituted ferrocenes. The oxidation of the ferrocene derivatives showed clear substituent effects as illustrated by the linear Hammett plots. The effect was shown to be an order of magnitude larger in the arylthio-systems than in the styryl systems. It is suggested that the reason behind the large effect is a direct sulfur-iron orbital overlap. Versita Sp. z o.o.
White light emission in water through admixtures of donor-π-acceptor siblings: Experiment and simulation
Kumari, Beena,Singh, Amit,Jana, Palash,Radhakrishna, Mithun,Kanvah, Sriram
, p. 11701 - 11709 (2019)
Donor-acceptor π-conjugated molecules with triphenylamine donor and different acceptor (H, cyano, and pyridinium) units with a double bond spacer were synthesized. These compounds exhibit bathochromic shifts in absorption and emission with an increase in the acceptor strength. Solvatochromic measurements in water reveal emitting states characterized by a polar nature with three distinct emission spectral regions from blue to red. Interestingly, binary mixtures of the stilbenes in acetonitrile and water gave white light emission. MD simulations of the admixtures reveal that the emission data directly correlate to the structural arrangements of the molecules driven by intermolecular and solvent interactions with micelle-like structural arrangements for one set and uniform homogenous mixing for the other two sets. Such a tunable emission strategy using simple structural siblings could offer great potential towards designing novel emitting systems.
Photo-Arbuzov Rearrangements of Benzyl Phosphites
Omelanzcuk, Jan,Sopchik, Alan E.,Lee, Sueg-Geun,Akutagawa, Kunihiko,Cairns, Matthew S.,Bentrude, Wesley G.
, p. 6908 - 6909 (1988)
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Copper-catalyzed synthesis of alkylphosphonates from H-phosphonates and N-tosylhydrazones
Miao, Wenjun,Gao, Yuzhen,Li, Xueqin,Gao, Yuxing,Tang, Guo,Zhao, Yufen
, p. 2659 - 2664 (2012)
A new catalytic system for the alkylation of H-phosphonates and diphenylphosphine oxide with N-tosylhydrazones has been developed. In the presence of copper(I) iodide and base, H-phosphonates react with N-tosylhydrazones to afford the corresponding coupled alkylphosphonates in good to excellent yields without any ligands. Alkylphosphonates can also be prepared in a one-pot process directly from carbonyl compounds without the isolation of tosylhydrazone intermediates.
Two trans-1-(9-anthryl)-2-phenylethene derivatives as blue-green emitting materials for highly bright organic light-emitting diodes application
Zhou, Nonglin,Shao, Xiaona,Wang, Shirong,Xiao, Yin,Li, Xianggao
, p. 228 - 238 (2017)
1-(9-Anthryl)-2-phenylethene (t-APE) is a blue-green material with high fluorescence quantum yield (Фf 0.44). However, it is easily crystallized. Herein, Two asymmetric blue-green emitting materials based on t-APE, (E)-9-(4-(2-(anthracen-9-yl)vinyl)phenyl)-10-(naphthalen-1-yl)anthracene (6) and (E)-9-(4-(2-(anthracen-9-yl)vinyl)phenyl)-10-(naphthalen-2-yl)anthracene (7) were firstly designed and synthesized. The two compounds possess high thermal stability, morphological durability, and bipolar characteristics. The non-doped blue-green organic light-emitting diodes (OLEDs) using 6 and 7 as emitting layers showed emission at 495 nm, full width at half maximum of 80 nm, maximum brightness of 13,814, 10,579 cd m?2, maximum current efficiency of 3.62, 7.16 cd A?1, and Commission Internationale de L'Eclairage (CIE) coordinate of (0.20, 0.43), respectively. Furthermore, when employing 6 and 7 as blue-green emitting layers and rubrene doped in tris-(8-hydroxyquinolinato)aluminum (Alq3) as the orange emitting layers to fabricate white OLEDs (WOLEDs), the WOLEDs exhibit a maximum brightness of 10,984, 14,652 cd m?2, maximum current efficiency of 2.04, 2.70 cd A?1, and CIE coordinate of (0.30, 0.40), (0.37, 0.47), Color Rendering Index (CRI) of 65, 60, stable EL spectra, respectively. This study demonstrates that the t-APE-type derivatives have the excellent properties for the emitting materials of OLEDs.
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Rabinowitz,R.
, p. 2975 - 2978 (1963)
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Microwave irradiation in organophosphorus chemistry. III. Moderate scale synthesis of reagents for olefin formation
Kiddle
, p. 3377 - 3382 (2001)
Representative phosphonates and phosphonium salts have been prepared on a moderate scale (25-50 g) using a domestic microwave oven. The reactions, conducted in sealed hydrogenation vessels, showed remarkable rate acceleration and excellent yields (>95%) employing this methodology.
Palladium-catalyzed copper(I) salt-mediated arylation of a bis(dimethylamino)phosphonyl-stabilized carbanion
Tarasenko, Elena A.,Lukashev, Nikolai V.,Beletskaya, Irina P.
, p. 1611 - 1613 (2000)
The synthesis of new arylmethylphosphonic acid tetramethyl diamides by a palladium-catalyzed cross-coupling reaction of a bis(dimethylamino)phosphonylmethylcopper(I) reagent with aryl iodides is described. (C) 2000 Elsevier Science Ltd.
Color tuning of doped PLEDs by energy transfer from PVK to dopant constituted with biphenyl and butadienyl unit
Han, Yoon Soo,Kim, Hoyoung,Choi, Byeong Dae,Kwon, Younghwan,Hur, Youngjune,Kwak, Giseop,Kim, Soon Hak,Park, Lee Soon,Choi, Byeong-Dae
, p. 341 - 351 (2007)
A dopant, 4,4'-bis(dimethyl[4-(2-phenyl-buta-1,3-dienyl)phenyl]amine) biphenyl (BPAB), was synthesized, and single layered polymer light emitting diode (PLED)s, ITO/Host:Dopant/Al, were fabricated with blends of poly(vinyl carbazole) (PVK) as host and BPAB as dopant. The electroluminescence (EL) was observed in doped PLEDs. From the EL and photoluminescence (PL) spectra, the existence of energy transfer from host to dopant was verified. With increasing content of dopant (BPAB), blue emission originated from PVK reduced, but didn't completely disappear, suggesting inefficient energy transfer from PVK to BPAB. When the content of BPAB was 15 wt%, yellow green emission from PLED was observed due to partial energy transfer from PVK to BPAB.
Identification of novel non-nucleoside vinyl-stilbene analogs as potent norovirus replication inhibitors with a potential host-targeting mechanism
Harmalkar, Dipesh S.,Lee, Sung-Jin,Lu, Qili,Kim, Mi Il,Park, Jaehyung,Lee, Hwayoung,Park, Minkyung,Lee, Ahrim,Lee, Choongho,Lee, Kyeong
, (2019)
Norovirus (NV), is the most common cause of acute gastroenteritis worldwide. To date, there is no specific anti-NV drug or vaccine to treat NV infections. In this study, we evaluated the inhibitory effect of different stilbene-based analogs on RNA genome replication of human NV (HNV) using a virus replicon-bearing cell line (HG23). Initial screening of our in-house chemical library against NV led to the identification of a hit containing stilbene scaffold 5 which on initial optimization gave us a vinyl stilbene compound 16c (EC50 = 4.4 μM). Herein we report our structure-activity relationship study of the novel series of vinyl stilbene analogs that inhibits viral RNA genome replication in a human NV-specific manner. Among these newly synthesized compounds, several amide derivatives of vinyl stilbenes exhibited potent anti-NV activity with EC50 values ranging from 1 to 2 μM. A trans-vinyl stilbenoid with an appended substituted piperazine amide (18k), exhibited potent anti-NV activity and also displayed favorable metabolic stability. Compound 18k demonstrated an excellent safety profile, the highest suppressive effect, and was selective for HNV replication via a viral RNA polymerase-independent manner. Its potential host-targeting antiviral mechanism was further supported by specific activation of heat shock factor 1-dependent stress-inducible pathway by 18k. These results suggest that 18k might be a promising lead compound for developing novel NV inhibitors with the novel antiviral mechanism.
Determination and application of the excited-state substituent constants of pyridyl and substituted phenyl groups
Cao, Chao-Tun,Yan, Lu,Cao, Chenzhong
, (2021/05/21)
Thirty six 1-pyridyl-2-arylethenes XCH=CHArY (abbreviated XAEY) were synthesized, in which, X is 2-pyridyl, 3-pyridyl and 4-pyridyl and Y is OMe, Me, H, Br, Cl, F, CF3, and CN. Their ultraviolet absorption spectra were measured in anhydrous ethanol, and their wavelengths of absorption maximum λmax were recorded. Also, the 234 λmax values of 1-substituted phenyl-2-arylethylene compounds (XAEY, where X is substituted phenyl) were collected. The excited-state substituent constants (Formula presented.) of three pyridyl groups and 23 substituted phenyl groups (total of 26) were obtained by means of curve-fitting method. Taking the λmax values of 358 samples of bi-arylethene derivatives as a data set and 126 samples of bi-aryl Schiff bases (including nine compounds synthesized by this work) as another data set, quantitative correlation analyses were performed by employing the obtained (Formula presented.) as a parameter, and good results were obtained for the two data sets. The reliability of the obtained (Formula presented.) values was verified. The results of this paper can provide excited-state substituent constants for the study and application of optical properties of conjugated organic compounds containing aryl groups.
Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
Hosseini-Sarvari, Mona,Koohgard, Mehdi
, p. 5905 - 5911 (2021/07/12)
In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.
