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1.
The bench-stable cyclic hypervalent fluoroiodane reagent (1) is receiving increasing attention in fluorine chemistry because of its completely new reactivity. Fluorination mediated by reagent 1 generally requires activation by an exogenous Lewis acid. A more complete understanding of the Lewis acid activation model is thus paramount for the development of new strategies involving this reagent. Density functional theory (DFT) calculations herein demonstrate the generality of the “F-coordination” activation mechanism for reagent 1 that we recently showed to be favored over the commonly accepted “O-coordination” activation mechanism. 相似文献
2.
《中国化学快报》2022,33(11):4834-4837
Herein we report a new general method for one-step synthesis of four kinds of fluoroiodane(III) reagents by treating the corresponding aryl iodides with silver difluoride (AgF2). This is the first method applicable for the synthesis of all four fluoroiodane(III) reagents including p-iodotoluene difluoride (1), fluoro-benziodoxole (2), fluoro-benziodoxolone (3), and fluoro-N-acetylbenziodazole (4). AgF2 was firstly employed in the direct oxidative fluorination of iodobenzene and thus has shown its outstanding oxidation and fluorine-transfer ability. The use of AgF2 has improved the synthesis of fluoroiodane(III) reagents by shortening the reaction steps, avoiding the use of hazardous reagents, and simplifying the experimental operations. It was worth noting that we have developed the first one-step direct synthetic method for 3, while 3 can only be synthesized through Cl→F ligand exchange reaction previously. 相似文献
3.
Mild Silver‐Mediated Geminal Difluorination of Styrenes Using an Air‐ and Moisture‐Stable Fluoroiodane Reagent
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Nadia O. Ilchenko Dr. Boris O. A. Tasch Prof. Kálmán J. Szabó 《Angewandte Chemie (International ed. in English)》2014,53(47):12897-12901
An air‐ and moisture‐stable fluoroiodane in the presence of AgBF4 is suitable for selective geminal difluorination of styrenes under mild reaction conditions. One of the C? F bonds is formed by transfer of electrophilic fluorine from the hypervalent iodine reagent, while the other one arises from the tetrafluoroborate counterion of silver. Deuterium‐isotope‐labelling experiments and rearrangement of methyl styrene substrates suggest that the reaction proceeds through a phenonium ion intermediate. 相似文献
4.
Di-t-butyl chromate -(t-BuO)2CrO2, DTBC- has proven to be a potent and versatile oxidizing reagent, suitable for the direct introduction of a carbonyl group in an allylic position1. The compound was prepared for the first time by Wienhaus2 but Oppenauer3 introduced it as a new oxidizing reagent. DTBC is a crystalline compound with a melting point of 0°C3,4 and is never used as such but always in a solution of a non polar solvent. 相似文献
5.
Simple synthesis of mixed cellulose acylate phosphonates applying n-propyl phosphonic acid anhydride
Thomas Heinze Velina Sarbova Matilde Calado Vieira Nagel 《Cellulose (London, England)》2012,19(2):523-531
Cellulose mixed esters containing alkylphosphonate and carboxylate groups were prepared homogeneously by a new one-pot method
using n-propyl phosphonic acid anhydride (T3P?) in LiCl/N-methyl-2-pyrrolidone (NMP). n-Propyl phosphonic acid anhydride acts as both an activating agent for carboxylic acids and phosphonation reagent. Cellulose
mixed esters with DSacyl ranging from 1.4 to 1.8, and DSphos up to 0.7 could be prepared. The structure of the cellulose mixed esters was elucidated by FTIR- and NMR spectroscopy, as
well as by GPC and solubility tests. 相似文献
6.
Hossein Imanieh Shahriar Ghammamy Mir Mohammad Alavi Nikje Farhang Hosseini Zahra Shokri Aghbolagh Hoong‐Kun Fun Hamid Reza Khavasi Reza Kia 《Helvetica chimica acta》2011,94(12):2248-2255
Benzyl(triphenyl)phosphonium dichloroiodate (BTPPICl2), BnPh3P+(ICl2)?, is easily synthesized in a nearly quantitative yield by the addition of BnPh3P+Cl? to a CH2Cl2 solution of iodine monochloride (ICl). BnPh3P+Cl? can be prepared by the reaction of Ph3P and BnCl. The compound was characterized by physicochemical and spectroscopic methods (elemental analysis, FT‐IR, and 1H‐NMR). The use of phosphonium counterion improves the quality of the BTPPICl2 crystals. BTPPICl2 crystallizes in the monoclinic system, and its crystal and molecular structure has been determined at 100(1) K by X‐ray diffraction. The structure was solved by the direct method and had refined R value of 0.0637 for 699 reflections (I>2σ(I)), space group P21/n with a=12.4700(3), b=13.2196(3), c=14.4580(3) Å, β=102.6340(10)°, V=2325.67(9) Å3, and Z=4. The I‐atom is coordinated by two Cl‐atoms as ligands in a linear geometry. This compound is a versatile reagent for the efficient and selective iodination of organic substrates, in particular of aromatic phenols to the corresponding iodo compounds, under mild conditions. To assess the generality of method, a wide variety of phenols with electron‐donating and electron‐withdrawing substituents were studied. BTPPICl2 is a mild iodination reagent, which offers a new avenue for an expeditious iodination of phenols. The inexpensive, relatively non‐toxic reagent, and mild conditions are the positive features of the procedure and reagent. 相似文献
7.
《Tetrahedron: Asymmetry》2006,17(13):1931-1936
Hydroboration of commercially available (+)-2-carene (96% ee) with either BH2Cl·SMe2 or BCl3/Me3SiH, provides chemically pure B-chlorobis(2-isocaranyl)borane (2-dIcr2BCl) whereas B-bromobis(2-isocaranyl)borane (2-dIcr2BBr) could only be prepared by Matteson’s BBr3/Me3SiH procedure in high chemical yield and purity. The enantiomeric excess achieved with 2-dIcr2BCl (78%), was significantly higher than those realized with the previously explored reagent, dIpc2BCl (41%), especially for meso-cyclohexene oxide. The new reagent, 2-dIcr2BBr also showed considerable improvements in enantiomeric excesses, in the cases of meso-cyclopentene oxide (67%) and meso-cis-2,3-butene oxide (78%) than those achieved with the previously reported reagent, dIpc2BBr (57% and 61%, respectively). 相似文献
8.
《Journal of organometallic chemistry》2003,665(1-2):127-134
The reactions of a phosphavinyl Grignard reagent, [CyPC(But)MgCl(OEt2)] Cy=cyclohexyl, with a variety of main group 13, 14 and 16 mono-halide compounds have been investigated. When the Grignard reagent is reacted with bromocatecholborane the terminal phosphavinyl complex, [(C6H4O2)B{C(But)PCy}], is formed. Related terminal phosphavinyl tin and gallium complexes, [R3Sn{C(But)PCy}], R=Me or Bun and [IGa{C(But)PCy}2], have been prepared by similar routes. The reaction of the Grignard reagent with PhSeCl has afforded a new λ5,λ5-diphosphete, [{(But)CP(Cy)(SePh)}2], the mechanism of formation of which is discussed. The preparation of a phosphavinyl selenium compound, [(C8H4O2N)PC(But)(SePh)], is also described. All compounds have been spectroscopically characterised and several have been crystallographically authenticated. 相似文献
9.
Kenza Richards Eddy Petit Yves-Marie Legrand Dr. Claude Grison 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):809-814
A new sustainable method is reported for the formation of aromatic carbon–heteroatom bonds under solvent-free and mild conditions (no co-oxidant, no strong acid and no toxic reagents) by using a new type of green ionic liquid. The bromination of methoxy arenes was chosen as a model reaction. The reaction methodology is based on only using natural sodium bromine, which is transformed into an electrophilic brominating reagent within an ionic liquid, easily prepared from the melted salt FeCl3 hexahydrate. Bromination reactions with this in-situ-generated reagent gave good yields and excellent regioselectivity under simple and environmentally friendly conditions. To understand the unusual bromine polarity reversal of sodium bromine without any strong oxidant, the molecular structure of the reaction medium was characterised by Raman and direct infusion electrospray ionisation mass spectroscopy (ESI-MS). An extensive computational investigation using density functional theory methods was performed to describe a mechanism that suggests indirect oxidation of Br− through new iron adducts. The versatility of the methodology was successively applied to nitration and thiocyanation of methoxy arenes using KNO3 and KSCN in melted hexahydrated FeCl3. 相似文献
10.
Ravi Gukathasan Indranil Gupta Siegmar Pulst Yogesh S. Sanghvi Scott A. Laneman 《Journal of organometallic chemistry》2005,690(10):2603-2607
A large-scale, cost-effective, and environmentally clean synthesis of high purity 2-cyanoethyl-N,N,N′,N′-tetraisopropylphosphorodiamidite (Phos reagent) has been accomplished on a commercial scale. Treatment of PCl3 with diisopropylamine followed by 3-hydroxylpropionitrile furnished the Phos reagent in excellent yield. The 31P NMR of the Phos reagent prepared at large-scale show consistent purities >99% when several key factors are controlled. These controlling factors include sourcing high purity key raw materials, identification and elimination of critical impurities, stability and storage of Phos reagent. 相似文献
11.
Clifford D. Juengst William P. Weber 《Journal of polymer science. Part A, Polymer chemistry》1987,25(7):1967-1978
Dimethyl phosphonomethylheptamethylcyclotetrasiloxane (II) and 1, 3-bis(dimethyl phosphonomethyl)tetramethyldisiloxane (III) have been prepared by Arbuzov reaction of trimethyl phosphite with bromomethylheptamethylcyclotetrasiloxane (I) and 1, 3-bis(bromomethyl)tetramethyldisiloxane, respectively. Dimethyl phosphonomethylmethylsiloxane dimethylsiloxane copolymers have been prepared by acid-catalyzed ring-opening polymerization of II with hexamethyldisiloxane (MM) as an end-capping reagent and by reaction of II with III as an end-capping reagent. Dimethylsiloxane polymers with dimethyl phosphonomethyldimethylsiloxy end groups have been prepared by acid-catalyzed polymerization of octamethylcyclotetrasiloxane (D4) and III. Under these conditions hydrolysis of the dimethyl phosphonate ester groups was a problem. On the other hand Arbuzov reaction of trimethyl phosphite with bromomethylmethylsiloxane dimethylsiloxane copolymer gave a dimethyl phosphonomethylmethylsiloxane dimethylsiloxane copolymer with uniform properties. These polymers have been characterized by 1H-, 13C-, 29Si-, and 31P-NMR spectroscopy. Their molecular weight distributions have been determined by gel permeation chromatography (GPC) and their thermal stability measured by TGA. 相似文献
12.
A new approach to 1‐phosphabicyclo[3.3.0]octane compounds starts from the reaction of 4‐chloro‐hepta‐1.6‐diene with Mg in THF. No Grignard rearrangement is observed. The Grignard reagent is converted into 1‐allyl‐3‐butenylphosphonous dichloride followed by reduction with LiAlH4. Cis‐1‐phosphabicyclo[3.3.0]octane has been prepared by radical‐initiated cyclization of 1‐allyl‐3‐butenylphosphane. The bicyclic phosphane is characterized by analytical data as well as 31P and 13C NMR measurements and the reactionswith NO, S8, KSeCN, CH3I, Ni(CO)4 and HSO3F, respectively. 相似文献
13.
Dingrong Deng Dr. Yanjun Zhang Gen Li Xueyun Wang Dr. Li‐Hua Gan Dr. Li Jiang Prof. Chun‐Ru Wang 《化学:亚洲杂志》2014,9(5):1265-1269
Nanometer‐sized flakes of MnV2O6 were synthesized by a hydrothermal method. No surfactant, expensive metal salt, or alkali reagent was used. These MnV2O6 nanoflakes present a high discharge capacity of 768 mA h g?1 at 200 mA g?1, good rate capacity, and excellent cycling stability. Further investigation demonstrates that the nanoflake structure and the specific crystal structure make the prepared MnV2O6 a suitable material for lithium‐ion batteries. 相似文献
14.
Mingzhe Jia Fenfen Liang Jiao Jiao Shuoqi Li Jingbo Hu 《Journal of Solid State Electrochemistry》2013,17(3):655-660
In this paper, a gold nanoparticle-modified indium tin oxide electrode (Au/ITO) was prepared without the use of any cross-linker or stabilizer reagent. The prepared Au/ITO was used as a new platform to achieve the direct electron transfer between Hb and the modified electrode. The proposed electrode exhibited a pair of well-defined redox peaks with a formal potential of ?0.073 V (vs. Ag/AgCl). The immobilized Hb showed excellent electrocatalytic activity toward H2O2 and the electrocatalytic current values were linear with the increasing concentration of H2O2 ranging from 1.0?×?10?6?M to 7.0?×?10?4?M. The detection limit was 2.0?×?10?7?M (S/N?=?3) and the Michaelis–Menten constant was calculated to be 0.2 mM. The proposed electrode also showed high selectivity, long-term stability, and good reproducibility. 相似文献
15.
纳米氧化镁具有不同于本体材料的光、电、磁、化学特性,特别是超细纳米氧化镁由于其颗粒直径小、比表面积大,具有高纯度、高硬度和高熔点,高的反应活性,强吸附性,良好的低温烧结性,高电阻率等优良性质,可用于高绝缘材料,高质量的陶瓷材料,高性能阻燃纤维,环境保护的吸附剂、负载型甲醇和低碳醇合成的催化剂载体等领域,是一种有广泛应用价值的新型无机材料[1 ̄5]。已见报道的纳米氧化镁的制备方法有电子束蒸发法[6]、化学气相沉积法[7]、金属醇盐水解法,化学沉淀法[8,9],固相法[10],燃烧法[11],溶胶-凝胶法[12,13]等,然而由于氧化镁容易发生… 相似文献
16.
Intermolecular Amination of Unactivated C(sp3)−H Bonds with Cyclic Alkylamines: Formation of C(sp3)−N Bonds through Copper/Oxygen‐Mediated C(sp3)−H/N−H Activation
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Quan Gou Yu‐Wen Yang Zi‐Ning Liu Prof. Jun Qin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(45):16057-16061
The first example of intermolecular amination of unactivated C(sp3)?H bonds by cyclic alkylamines mediated by Cu(OAc)2/O2 is reported. This method avoids the use of benzoyloxyamines as the aminating reagent, which are normally prepared from alkylamines in extra steps. A variety of unnatural β2, 2‐amino acid analogues are synthesized by this simple and efficient procedure. This approach offers a solution to the previous unmet challenge of C(sp3)?H/N?H activation for the formation of C(sp3)?N bonds. 相似文献
17.
Heng-dao Quan Hui-e Yang Masanori Tamura Akira Sekiya 《Journal of fluorine chemistry》2004,125(7):1169-1172
A novel fluorination reagent and catalyst, SbF5/PAF (porous aluminum fluoride), was prepared by impregnating SbCl5 into PAF and then treating with anhydrous hydrogen fluoride. The prepared reagent had an excellent catalytic activity in halogen-exchange, and also improved the properties of SbF5, such as hydroscopicity, corrosion, and toxicity. SbF5/PAF was successfully used in organic synthesis as a fluorinating reagent, and a fixed bed catalyst for F/Cl exchange. 相似文献
18.
《Arabian Journal of Chemistry》2014,7(6):1017-1023
New aromatic diamine monomers prepared from condensation reactions of aniline, p-chloroaniline, p-nitro aniline, p-chloro-m-nitro aniline with 4-amino-N,N-dimethylaniline (2:1) (aniline:reagent) in the presence of potassium dichromate in acidic media yielded new monomers of a highly colored violet and reddish-violet. Mechanism of the reaction of aniline with 4-amino-N,N-dimethylaniline in the presence of potassium dichromate as an oxidant is expected to proceed through nucleophilic substitution reaction, and the mechanism proceeds facilitated a nucleophilic attack of the substituted aniline ring on the –NH2 group of the reagent; through partial protonation of their –NH2 group, forming in diamine dye and their identification was confirmed by IR, 1H NMR, and CHN analyses. 相似文献
19.
Jiang Wu Qunchao Zhao Thomas C. Wilson Stefan Verhoog Long Lu Vronique Gouverneur Qilong Shen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(8):2435-2439
A highly reactive electrophilic bromodifluoromethylthiolating reagent, α‐cumyl bromodifluoro‐methanesulfenate 1 , was prepared to allow for direct bromodifluoromethylthiolation of aryl boron reagents. This coupling reaction takes place under copper catalysis, and affords a large range of bromodifluoromethylthiolated arenes. These compounds are amenable to various transformations including halogen exchange with [18F]KF/K222 , a process giving access to [18F]arylSCF3 in two steps from the corresponding aryl boronic pinacol esters. 相似文献
20.
A novel Ti(Oi‐Pr)4 mediated olifination between Julia reagent and aldehydes has been developed. By this method, a series of substituted vinyl sulfones are prepared under mild conditions, all products are exclusively E isomers. All the structures of these compounds were confirmed by 1H NMR, 13C NMR HRMS and IR. 相似文献