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151.
152.
ABSTRACTThe reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH2) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10?13?cm3?molecule?1?s?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10?13?cm3?molecule?1?s?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH2 is 1.71?×?10?15?cm3?molecule?1?s?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH3. 相似文献
153.
Weihua Zhou Zoukangning Yu Ming Zhang Lifu Zhang Jingping Yin Qingyun Ai Liqiang Huang Feng Liu Jianrong Zeng Yiwang Chen 《Journal of Polymer Science.Polymer Physics》2019,57(14):941-951
In order to explore the role of fluorine atoms on photostability as well as morphology control of active layer in the presence of 1,4‐butanedithiol (BT), the four polymers with or without fluorine atoms in the backbones including polythieno[3,4‐b]thiophene/benzodithiophene, poly[(4,8‐bis‐(2‐ethylhexyloxy)‐benzo(1,2‐b:4,5‐b9)dithiophene)‐2,6‐diyl‐alt‐(4‐(2‐ethylhexanoyl)‐thieno[3,4‐b]thiophene‐)‐2‐6‐diyl)], poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)], and poly[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b0]dithiophene‐2,6‐diyl]‐alt‐[2‐(20‐ethyl‐hexanoyl)‐thieno [3,4‐b]thiophen‐4,6‐diyl] were selected for comparison. It is found that the specimens containing fluorine atoms in polymer backbones showed of higher stability after illumination for 1 h in the presence of BT additive, contributing to the higher domain purity. The specific interaction between fluorine atoms and thiol groups was demonstrated by the appearance of novel absorption peak at 2663.1 cm?1, in addition to the broadening of peak at 2556.2 cm?1 ascribing to S? H stretching vibration as confirmed by Fourier transform infrared (FTIR) spectroscopy. The finding may guide the accurate use of thiols as effective solvent additive in morphology and stability optimization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 941–951 相似文献
154.
Ikhlas Gadwal Prakash P. Wadgaonkar Amol B. Ichake Shivshankar R. Mane 《Journal of polymer science. Part A, Polymer chemistry》2019,57(2):146-156
A new approach was developed for synthesis of certain A3B3‐type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of “grafting onto” and “grafting from” methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (Mn = 550 and 2000 g mol?1) were utilized to generate A3‐type of homoarm star polymers through an in situ protective group removal and a subsequent thiol–epoxy “click” reaction with a tris‐epoxide core viz. 1,1,1‐tris(4‐hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol–epoxy reaction were esterified with α‐bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N‐isopropylacrylamide (NIPAM) using the three‐arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A3B3‐type of double hydrophilic (PEG)3[poly(N‐isopropylacrylamide)] (PNIPAM)3 miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring‐opening polymerization of ε‐caprolactone to prepare A3B3‐type of amphiphilic (PEG)3[poly(ε‐caprolactone)]3 miktoarm star polymers. The double hydrophilic (PEG)3(PNIPAM)3 miktoarm star polymers showed lower critical solution temperature around 34 °C. The preliminary transmission electron microscopy analysis indicated formation of self‐assembly of (PEG)3(PNIPAM)3 miktoarm star polymer in aqueous solution. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 146–156 相似文献
155.
《Journal of computational chemistry》2017,38(13):981-997
A novel approach for calculating deformation densities is presented, which enables to calculate the deformation density resulting from a change between two chemical states, typically conformers, without the need for radical fragments. The Fragment, Atom, Localized, Delocalized, and Interatomic (FALDI) charge density decomposition scheme is introduced, which is applicable to static electron densities (FALDI‐ED), conformational deformation densities (FALDI‐DD) as well as orthodox fragment‐based deformation densities. The formation of an intramolecular NH⋅⋅⋅N interaction in protonated ethylene diamine is used as a case study where the FALDI‐based conformational deformation densities (with atomic or fragment resolution) are compared with an orthodox EDA‐based approach. Atomic and fragment deformation densities revealed in real‐space details that (i) pointed at the origin of density changes associated with the intramolecular H‐bond formation and (ii) fully support the IUPAC H‐bond representation. The FALDI scheme is equally applicable to intra‐ and intermolecular interactions. © 2017 Wiley Periodicals, Inc. 相似文献
156.
157.
Peng Yang Yaxin Sun Kaiyue Fu Li Zhang Guang Yang Jieyu Yue Yu Ma Jianrong Steve Zhou Bo Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202111778
We report a stereoselective conversion of terminal alkynes to α-chiral carboxylic acids using a nickel-catalyzed domino hydrocarboxylation-transfer hydrogenation reaction. A simple nickel/BenzP* catalyst displayed high activity in both steps of regioselective hydrocarboxylation of alkynes and subsequent asymmetric transfer hydrogenation. The reaction was successfully applied in enantioselective preparation of three nonsteroidal anti-inflammatory profens (>90 % ees) and the chiral fragment of AZD2716. 相似文献
158.
Dr. Christine Beemelmanns Dr. Dominik Nitsch Dr. Christoph Bentz Prof. Dr. Hans-Ulrich Reissig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8780-8789
A series of γ-indolylketones with fluorine, cyano or alkoxy substituents at the benzene moiety was prepared and subjected to samarium diiodide-promoted cyclization reactions. The desired dearomatizing ketyl cascade reaction forming two new rings proceeded in all cases with high diastereoselectivity, but with differing product distribution. In most cases, the desired annulated tetracyclic compounds were obtained in moderate to good yields, but as second product tetracyclic spirolactones were isolated in up to 29 % yield. The reaction rate was influenced by the substituents at the benzene moiety of the substrate as expected, with electron-accepting groups accelerating and electron-donating groups decelerating the cyclization process. In case of a difluoro-substituted γ-indolylketone a partial defluorination was observed. The intermediate samarium enolate of the tetracyclic products could be trapped by adding reactive alkylating agents as electrophiles delivering products with quarternary carbons. In the case of a dimethoxy-substituted tetracyclic cyclization product a subsequent reductive amination stereoselectively provided a pentacyclic compound that was subsequently N-protected and subjected to a regioselective elimination. The obtained functionalized pentacyclic product should be convertible into the alkaloid brucine by four well-established steps. Overall, the presented report shows that functionalized tetracyclic compounds with different substituents are rapidly available with the samarium diiodide cascade cyclization as crucial step. Hence, analogues of the landmark alkaloid strychnine, for example, with specific fluorine substitutions, should be easily accessible. 相似文献
159.
Huatian Shi Jianhui Xie William W. Y. Lam Wai-Lun Man Chi-Keung Mak Shek-Man Yiu Hung Kay Lee Tai-Chu Lau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12895-12899
The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [MnV(TAML)(N-Mes)]− ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC6H4)3N ]+.[SbCl6]− and the resulting MnVI species readily undergoes H-atom transfer and nitrene transfer reactions. 相似文献
160.
Butylated hydroxytoluene enediyne: access to diradical and electrophilic quinone methide intermediates
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Edyta M. Greer Cesar S. Quezada Christopher V. Cosgriff 《Journal of Physical Organic Chemistry》2015,28(5):365-369
A theoretical study was carried out on the unimolecular reaction of an enediyne with a fused butylated hydroxytoluene to internally scavenge the p‐benzyne diradical sites formed after the Bergman cyclization. The calculations revealed that the conversion of the p‐benzyne diradical (2‐tert‐butyl‐4‐methyl‐5,8‐didehydro‐1‐naphthalenol) to p‐quinone methide is favored over the conversion to a phenoxy/benzene diradical 4 in an approximate 95:5 ratio. Based on this model, the Bergman cyclization leads in a bifunctional manner to intermediates for competing reactivity with intermolecular H‐atom abstraction. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献