排序方式: 共有83条查询结果,搜索用时 15 毫秒
1.
Apparent molal heat capacities
of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry
in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental
values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions
between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of
ΔC
p
for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined. 相似文献
2.
Cossy J 《Chemical record (New York, N.Y.)》2005,5(2):70-80
The synthesis of optically active substituted piperidines has been achieved by using four different methodologies. The first one is an intramolecular nucleophilic displacement of activated alcohol moieties that was used to build up the piperidine ring of (-)-prosophylline and (-)-slaframine, and the second one is a ring-closing metathesis of unsaturated amines which was employed in the synthesis of (+)-sedamine and 4a,5-dihydrostreptazoline. The third methodology is the alpha-functionalization of N-Boc piperidines which was particularly useful in the synthesis of argatroban, and the fourth one is a ring expansion of prolinols to 3-chloropiperidines or 3-hydroxypiperidines which was utilized to synthesize (-)-paroxetine, (-)-pseudoconhydrine, the piperidine ring of (-)-velbanamine and (+)-zamifenacin. 相似文献
3.
Alain Merschaert Laurent DelhayeJean-Paul Kestemont Willy BrionePieter Delbeke Vincent MancusoFreddy Napora Khalid DikerDaniel Giraud Michel Vanmarsenille 《Tetrahedron letters》2003,44(24):4531-4534
A stereoselective approach has been developed for the synthesis of cis- and trans-2-methyl-4-arylpiperidines from a common intermediate. The Ni-catalyzed hydrogenolysis of N-Boc-2-methyl-4-aryl-4-piperidinols, obtained by addition of organometallic reagents on N-Boc-2-methyl-4-piperidone, afforded the trans derivatives with up to 95% selectivity whereas the corresponding cis isomers were obtained in the presence of palladium catalysts. 相似文献
4.
The values of partial molar free energy (G), enthalpy (H), and entropy (S) of sorption in the homologous series ofN-alkylpiperidines,N-alkylmorpholines,N-alkyl thiomorpholines, and alkylcyclohexanes were determined. It was found that the free energy of sorption is determined to a greater extent by the enthalpy term than by the entropy one. The free energy of sorption of the first homolog decreases when then-alkyl chain is attached directly to the carbon atom of the cycle and increases in the case ofN-alkylsubstituted heterocycles. The influence of the heteroatom nature on intermolecular interactions of homologs with the nonpolar stationary phase was quantitatively estimated on the basis of thermodynamic data.Dead time necessary for calculation of the retention factor was determined by the retention of methane injected into the column simultaneously with the sample.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2030–2032, August, 1996. 相似文献
5.
6.
Access to Optically Active 3‐Substituted Piperidines by Ring Expansion of Prolinols and Derivatives
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Domingo Gomez Pardo Prof. Janine Cossy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4516-4525
The ring expansion of prolinols via an aziridinium intermediate gives C3‐substituted piperidines in good yields and enantiomeric excess, the substituent at the C3 position being derived from the most reactive nucleophile in the reaction mixture. Depending on the nucleophile, the reaction proceeds under thermodynamic or kinetic control. The regioselectivity of attack of nucleophiles on the aziridinium intermediate depends on the nature of the substituents on the nitrogen atom and the C4 position of the starting prolinols. 相似文献
7.
Fully Diastereoselective Synthesis of Polysubstituted,Functionalized Piperidines and Decahydroquinolines Based on Multicomponent Reactions Catalyzed by Cerium(IV) Ammonium Nitrate
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Padmakar A. Suryavanshi Dr. Vellaisamy Sridharan Dr. Swarupananda Maiti Prof. J. Carlos Menéndez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8791-8799
The cerium(IV) ammonium nitrate (CAN)‐catalyzed, three‐component reaction between primary amines, β‐dicarbonyl compounds, and α,β‐unsaturated aldehydes in ethanol heated to reflux, constitutes a general, one‐pot synthesis of 1,4‐dihydropyridines. Their reduction with sodium triacetoxyborohydride furnished piperidine derivatives bearing up to five substituents with full diastereoselectivity in a hitherto inaccessible stereochemical arrangement. The reaction proceeded with no significant loss of enantiomeric purity under mild reduction conditions that are compatible with several functional groups that are normally sensitive to reduction. Octahydroquinolin‐5‐one derivatives, which were prepared by a modified version of the initial multicomponent reaction, were not suitable substrates for the sodium triacetoxyborohydride mediated reduction, but they were transformed into the corresponding decahydroquinolines, including a precursor of the amphibian alkaloid pumiliotoxin C, by catalytic hydrogenation under a variety of conditions. 相似文献
8.
Sumin Lee Natthawat Semakul Tomislav Rovis 《Angewandte Chemie (International ed. in English)》2020,59(12):4965-4969
We report a RhIII‐catalyzed regio‐ and diastereoselective synthesis of δ‐lactams from readily available acrylamide derivatives and unactivated alkenes. The reaction provides a rapid route to a diverse set of δ‐lactams in good yield and stereoselectivity, which serve as useful building blocks for substituted piperidines. The regioselectivity of the reaction with unactivated terminal alkene is significantly improved by using Cpt ligand on the RhIII catalyst. The synthetic utility of the reaction is demonstrated by the preparation of a potential drug candidate containing a trisubstituted piperidine moiety. Mechanistic studies show that the reversibility of the C?H activation depends on the choice of Cp ligand on the RhIII catalyst. The irreversible C?H activation is observed and becomes turnover‐limiting with [CptRhCl2]2 as catalyst. 相似文献
9.
Chuanqi Hou Pinhong Chen Guosheng Liu 《Angewandte Chemie (International ed. in English)》2020,59(7):2735-2739
The first asymmetric PdII‐catalyzed aminofluorination of unactivated alkenes using chiral quinoline‐oxazolines (Quox) as ligands has been developed. This reaction provides easy access to a wide array of enantiomerically enriched β‐fluoropiperidines in good yields and with excellent enantioselectivity. Notably, Et4NF?3 HF as a readily accessible nucleophilic fluoride source was found to play an essential role in the enantioselective control, and CsOCF3 also acts a key additive to improve the excellent ee value of products. 相似文献
10.
The standard partial molar free energies, enthalpies, and entropies of sorption of the methylene units in the homologous series
of alkylcyclohexanes andN-alkylsubstituted sixmembered heterocycles (piperidines, morpholines, and thiomorpholines) were determined on a capillary
column with the methylsiloxane OV-101 stationary phase at 70–150°C. A characteristic feature of all series under study is
an abnormally high increase in the values of thermodynamic parameters of sorption on going from the methyl to the ethyl homolog.
This peculiarity is believed to be associated with the presence of thegauche butane orgauche methylethylamine fragments in the ethyl homolog. Thesegauche fragments have an increased sorption activity under conditions of gas chromatography in comparison with the correspondingtrans form.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 500–503, March, 1997. 相似文献