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排序方式: 共有115条查询结果,搜索用时 15 毫秒
1.
Malassene R Vanquelef E Toupet L Hurvois JP Moinet C 《Organic & biomolecular chemistry》2003,1(3):547-551
The anodic cyanation of methanolic solutions of the 2-alkyl-N-phenylpiperidines 6b-d was performed in a flow cell equipped with a graphite felt anode. The reaction led to the formation of the 2-cyano-6-alkyl-N-phenylpiperidines 2b-d and proceeded with a high degree of regioselectivity. The 1H NMR spectra of the aminonitriles 2b-d showed an epimeric mixture at C-6. The major isomer has a trans configuration in which the cyano group is axial and the alkyl substituent is equatorial. Conversely, electrochemical oxidation of the 4-methyl-6-pentyl-N-phenylpiperidine 6e afforded the trisubstituted aminonitrile 2e as a single diastereomer (> 98% de). The 4-cyanobutyl side chain was incorporated in a two-step procedure to yield dinitrile 4e. This latter compound was directly converted into spiropiperidine 5e by using the Thorpe-Ziegler annulation procedure. The overall sequence (4 steps, 43%) allows the construction of the basic carbon framework of perhydrohistrionicotoxin. 相似文献
2.
James Courmarcel Gildas Le Gland Loic Toupet Fr d ric Paul Claude Lapinte 《Journal of organometallic chemistry》2003,670(1-2):108-122
The synthesis of the new (η2-dppe)(η5-C5Me5)Fe---CC---1,3-(C6H4X) (m-2a/2b; X=F/Br) and (η2-dppe)(η5-C5Me5)Fe---CC---1,4-(C6H4I) (2c) complexes, as well as the solid-state structure of the known (η2-dppe)(η5-C5Me5)Fe---CC---1,4-(C6H4F) (2a) complex are described. The catalytic coupling reactions of the bromo complexes with various alkynes were next investigated. Starting from the known (η2-dppe)(η5-C5Me5)Fe---CC---1,4-(C6H4Br) complex (2b), the synthesis of the (η2-dppe)(η5-C5Me5)Fe---CC---1,4-(C6H4)---CC---H complex (6d) and of the corresponding silyl-protected precursors (η2-dppe)(η5-C5Me5)Fe---CC---1,4-(C6H4)CC---SiR3 (6b/6c; R=iPr/Me) are reported. By use of lithium---bromine exchange reactions on 2b, the silyl- (7a; E=Si; R=Me) and tin- (7b–7d; E=Sn; R=Me, Bu, Ph) substituted analogues (η2-dppe)(η5-C5Me5)Fe---CC---1,4-(C6H4)ER3 are also isolated. The spectroscopic and electrochemical characterisations of all these new Fe(II)/Fe(III) redox-active building blocks are presented and the electronic substituent parameters for the “(η2-dppe)(η5-C5Me5)Fe---CC” group are determined by means of 19F-NMR. 相似文献
3.
The crystal and molecular structures of three simple porphyrin diacids have been determined from X-ray diffraction data to delineate how the peripheral substituents of the porphyrin affect the overall molecular flexibility. Di-meso-substituted [DPPH4]2+(CF3CO2−)2 and, mono-meso-substituted [MPPH4]2+(CF3CO2−)2 and [dedmMPPH4]2+(CF3CO2−)2 porphyrin diacids show increasingly saddled core conformation. Some of the spectroscopic properties (NMR and UV-visible) of the porphyrin diacids are also discussed in terms of the observed structures. 相似文献
4.
2,4-dichlorophenyl-4-bromomethyl-phenoxyacetate 3 was prepared by NBS treatement of 2,4-dichlorophenyl-4-methylphenoxyacetate 2. This ester is a key intermediate in the preparation of 2,4-dichlorophenyl-Nα-Fmoc-aminoacyl-4-oxymethylphenoxy-acetates suitable for anchorage of the first amino acid on amine-functionalized polymers. 相似文献
5.
Hang Chen Camel Tanougast Zhengjun Liu Loic Sieler Harry Ramenah 《Optical and Quantum Electronics》2017,49(4):157
A novel asymmetric cryptosystem for optical image is proposed using fingerprint based on iterative fractional Fourier transform. To enhance the security, a hyperchaotic phase generated by a 4D Lorenz system is considered as the public key in the proposed encryption system, while the private key is emerged by the retrieved phase and fingerprint. In the encryption process, the secret information is hid into the hyperchaotic phase. Subsequently, the private key can be obtained by a reversible operation. To decrypt the original image, the ciphertext and private key are imported into the input plane of fractional Fourier system. This system is also applicable for information authentication because the fingerprint is used both in encryption and decryption approach. Some numerical simulations have been done to test the validity and capability of the encryption system. 相似文献
6.
Dr. Sylvain Achelle Dr. Jean‐Pierre Malval Dr. Stéphane Aloïse Dr. Alberto Barsella Dr. Arnaud Spangenberg Dr. Loic Mager Dr. Huriye Akdas‐Kilig Dr. Jean‐Luc Fillaut Prof. Bertrand Caro Prof. Françoise Robin‐le Guen 《Chemphyschem》2013,14(12):2725-2736
The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching. 相似文献
7.
Spin‐State Ordering on One Sub‐lattice of a Mononuclear Iron(III) Spin Crossover Complex Exhibiting LIESST and TIESST 下载免费PDF全文
Dr. Kevin D. Murnaghan Dr. Chiara Carbonera Dr. Loic Toupet Dr. Michael Griffin Dr. Marinela M. Dîrtu Dr. Cédric Desplanches Prof. Dr. Yann Garcia Prof. Eric Collet Prof. Jean‐François Létard Dr. Grace G. Morgan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5613-5618
The two‐step spin crossover in mononuclear iron(III) complex [Fe(salpm)2]ClO4 ? 0.5 EtOH ( 1 ) is shown to be accompanied by a structural phase transition as concluded from 57Fe Mössbauer spectroscopy and single crystal X‐ray diffraction, with spin‐state ordering on just one of two sub‐lattices in the intermediate magnetic and structural phase. The complex also exhibits thermal‐ and light‐induced spin‐state trapping (TIESST and LIESST), and relaxation from the LIESST and TIESST excited states occurs via the broken symmetry intermediate phase. Two relaxation events are evident in both experiments, that is, two T(LIESST) and two T(TIESST) values are recorded. The change in symmetry which accompanies the TIESST effect was followed in real time using single crystal diffraction. After flash freezing at 15 K the crystal was warmed to 40 K at which temperature superstructure reflections were observed to appear and disappear within a 10 000 s time range. In the frame of the international year of crystallography, these results illustrate how X‐ray diffraction makes it possible to understand complex ordering phenomena. 相似文献
8.
Armspach D Poorters L Matt D Benmerad B Balegroune F Toupet L 《Organic & biomolecular chemistry》2005,3(14):2588-2592
1,3-Bis[bis(4-tert-butylphenyl)chloromethyl]benzene and 1,3-bis[bis(4-anisyl)chloromethyl]benzene were employed as regioselective capping reagents for the preparation of C-6A,C-6B-bridged, permethylated alpha- and beta-CD derivatives; isolated yields up to 55% of proximally capped, methylated CDs were obtained, thus opening the way to the straightforward preparation of a wide range of A,B-functionalised CDs. As revealed by a single crystal X-ray diffraction study, the benzene-1,3-bis[bis(4-tert-butylphenyl)methyl] spacer is perfectly suited for A,B-capping of beta-cyclodextrin. 相似文献
9.
10.
Henry-dit-Quesnel A Toupet L Pommelet JC Lequeux T 《Organic & biomolecular chemistry》2003,1(14):2486-2491
The synthesis of difluoromethylphosphonates is becoming difficult due to environmental protective laws restricting the use of HCFCs and CFCs as starting chemicals. To circumvent this limitation, we report the preparation of a thioether as a new source of the lithiodifluoromethylphosphonate. This methodology avoiding the use of HCFCs involves a selective fluorination of sulfide followed by a thiaphilic addition of an organometallic reagent, which offers an alternative route to obtain phosphonodifluoromethyl carbanion. A contrasted reactivity, due to a medium effect, was also noted which allows addition of a wide range of electrophiles including nitroalkenes and DMF to thioethers. 相似文献