Stereoselectivity in the Reactions between the Anion of 4-Phenyl-5,6-dihydro-2H-thiopyran 1-Oxide and Electrophiles

1985 ◽  
Vol 38 (1) ◽  
pp. 119 ◽  
Author(s):  
RL Crumbie ◽  
DD Ridley ◽  
PJ Steel
Keyword(s):  
Anion Exchange ◽  
Membered Ring ◽  
Alkyl Halides ◽  
Exchange Reactions ◽  
X Ray ◽  
Higher Temperature

Treatment of the anion(17), prepared from the six- membered ring allylic sulfoxide 4-phenyl-5,6-dihydro-2H-thiopyran 1-oxide (8) with primary alkyl halides at -78°, affords trans-2-alkyl-4-phenyl-5,6-dihydro-2H-thiopyran 1-oxides exclusively. The stereospecificity of these reactions thus corresponds to that obtained from the related saturated cyclic sulfoxides . However, when the anion (17) is treated with 2-iodopropane (-78° → 20°) a mixture of 2-cis and 2-trans products results. Independent experiments indicate that the lack of stereoselectivity is due to anion exchange reactions at the higher temperature required to effect alkylation. 2-cis and 2-trans Adducts also are obtained in reactions of the anion (17) with benzaldehydes (-78° → 0°), and from X-ray crystallographic analyses it has been established that the cis adducts predominate, with little selectivity in attack on the two enantiotopic faces of the aldehyde.

Unexpected Pyrolytic Behaviour of Substituted Benzo[c]thiopyran and Thieno[2,3-c]thiopyran S,S-dioxides

2014 ◽  
Vol 67 (9) ◽  
pp. 1288 ◽  
Author(s):  
R. Alan Aitken ◽  
Clémence Hauduc ◽  
M. Selim Hossain ◽  
Emily McHale ◽  
Adrian L. Schwan ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Ring Expansion ◽  
Hydrogen Atom Transfer ◽  
Membered Ring ◽  
X Ray ◽  
Flash Vacuum Pyrolysis ◽  
Vacuum Pyrolysis ◽  
Higher Temperature ◽  
Intramolecular Hydrogen ◽  
Carbonyl Products

Flash vacuum pyrolysis (FVP) of benzo[c]thiopyran S,S-dioxide (1) results in formation of indene and 2-vinylbenzaldehyde as previously described. A range of eight analogues with various substitution patterns are found to behave differently. In general, there is no extrusion of SO2 to give products analogous to indene, but unsaturated carbonyl products analogous to 2-vinylbenzaldehyde are formed in most cases by way of ring expansion to a 7-membered ring sultine, extrusion of SO, and intramolecular hydrogen atom transfer. Other processes observed include formation of anthracene via an isomeric 7-membered sultine with loss of SO, CO and methane or butane, and formation of 4-ethylidene-4,5-dihydrocyclobuta[b]thiophenes by way of SO loss, a radical rearrangement, and extrusion of acetone. The analogues with a halogen substituent at position 8 on the benzene ring require a higher temperature to react and give naphthalene resulting from net elimination of HX and SO2. The X-ray crystal structure of 1 is also reported.

scholarly journals X-ray Lithography on Perovskite Nanocrystals Films: From Patterning with Anion-Exchange Reactions to Enhanced Stability in Air and Water

ACS Nano ◽  
2015 ◽  
Vol 10 (1) ◽  
pp. 1224-1230 ◽  
Author(s):  
Francisco Palazon ◽  
Quinten A. Akkerman ◽  
Mirko Prato ◽  
Liberato Manna
Keyword(s):  
Anion Exchange ◽  
Exchange Reactions ◽  
Perovskite Nanocrystals ◽  
X Ray ◽  
Enhanced Stability

Application of In Situ X-ray Absorption Spectroscopy to Study Dilute Chromium Ions in a Molten Chloride Salt

2019 ◽  
Author(s):  
Jisue Moon ◽  
Carter Abney ◽  
Dmitriy Dolzhnikov ◽  
James M. Kurley ◽  
Kevin A. Beyer ◽  
...  
Keyword(s):  
Absorption Spectroscopy ◽  
Local Structure ◽  
Chloride Salt ◽  
X Ray ◽  
Molten Chloride ◽  
Stable Species ◽  
Higher Temperature ◽  
Cr Concentration ◽  
X Ray Absorption

The local structure of dilute CrCl<sub>3</sub> in a molten MgCl<sub>2</sub>:KCl salt was investigated by <i>in situ</i> x-ray absorption spectroscopy (XAS) at temperatures from room temperature to 800<sup>o</sup>C. This constitutes the first experiment where dilute Cr speciation is explored in a molten chloride salt, ostensibly due to the compounding challenges arising from a low Cr concentration in a matrix of heavy absorbers at extreme temperatures. CrCl<sub>3</sub> was confirmed to be the stable species between 200 and 500<sup>o</sup>C, while mobility of metal ions at higher temperature (>700<sup>o</sup>C) prevented confirmation of the local structure.

scholarly journals X-ray, DTA and Raman studies of monoclinic tridymite and its higher temperature orthorhombic modification with varying temperature

2005 ◽  
Vol 100 (2) ◽  
pp. 55-69 ◽  
Author(s):  
Tadayuki HIROSE ◽  
Kuniaki KIHARA ◽  
Masayuki OKUNO ◽  
Syuhei FUJINAMI ◽  
Keiji SHINODA
Keyword(s):  
X Ray ◽  
Orthorhombic Modification ◽  
Higher Temperature

scholarly journals Impact of high temperatures on aluminoceladonite studied by Mössbauer, Raman, X-ray diffraction and X-ray photoelectron spectroscopy

2021 ◽  
Author(s):  
Mariola Kądziołka-Gaweł ◽  
Maria Czaja ◽  
Mateusz Dulski ◽  
Tomasz Krzykawski ◽  
Magdalena Szubka
Keyword(s):  
Photoelectron Spectroscopy ◽  
Integral Intensity ◽  
Photoelectron Spectra ◽  
X Ray Diffraction ◽  
Structural Reorganization ◽  
Oh Groups ◽  
X Ray ◽  
Al Content ◽  
Integral Intensity Ratio ◽  
Higher Temperature

AbstractMössbauer, Raman, X-ray diffraction and X-ray photoelectron spectroscopies were used to examine the effects of temperature on the structure of two aluminoceladonite samples. The process of oxidation of Fe2+ to Fe3+ ions started at about 350 °C for the sample richer in Al and at 300 °C for the sample somewhat lower Al-content. Mössbauer results show that this process may be associated with dehydroxylation or even initiate it. The first stage of dehydroxylation takes place at a temperature > 350 °C when the adjacent OH groups are replaced with a single residual oxygen atom. Up to ~500 °C, Fe ions do not migrate from cis-octahedra to trans-octahedra sites, but the coordination number of polyhedra changes from six to five. This temperature can be treated as the second stage of dehydroxylation. The temperature dependence on the integral intensity ratio between bands centered at ~590 and 705 cm−1 (I590/I705) clearly reflects the temperature at which six-coordinated polyhedra are transformed into five-coordinated polyhedra. X-ray photoelectron spectra obtained in the region of the Si2p, Al2p, Fe2p, K2p and O1s core levels, highlighted a route to identify the position of Si, Al, K and Fe cations in a structure of layered silicates with temperature. All the measurements show that the sample with a higher aluminum content and a lower iron content in octahedral sites starts to undergo a structural reorganization at a relatively higher temperature than the less aluminum-rich sample does. This suggests that iron may perform an important role in the initiation of the dehydroxylation of aluminoceladonites.

Study of Low-Grade Nickel Laterite Processing Using Palm Shell Charcoal as Reductant

2020 ◽  
Vol 1000 ◽  
pp. 436-446
Author(s):  
Bambang Suharno ◽  
Nolzha Primadha Ilman ◽  
Achmad Shofi ◽  
Deni Ferdian ◽  
Fajar Nurjaman
Keyword(s):  
Sodium Sulfate ◽  
Selective Reduction ◽  
Reduction Process ◽  
Low Grade ◽  
X Ray Diffraction ◽  
X Ray ◽  
Palm Shell ◽  
Higher Temperature ◽  
Nickel Grade

This study was conducted to investigate the effect of palm shell charcoal reductant in the selective reduction of nickel ore with the addition of additive at various temperatures and times. In this present work, 10 wt. % of sodium sulfate as additive and 5, 10, 15 wt. % of palm shell charcoal as reductants were used. The reduction of nickel ore was performed at 950oC, 1050oC, and 1150oC for 60, 90, and 120 minutes. A wet magnetic separation method was then carried out to separate the concentrates and tailings. Characterization of reduced ore was performed by X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDS), while the composition of ferronickel in concentrate was identified by X-Ray Fluorescence (XRF). The result showed that the higher temperature reduction, the higher of nickel grade, and its recovery at the concentrate. Nevertheless, the longer reduction time and the more reductant in nickel ore lowering the nickel grade and its recovery in the concentrate. The optimum condition in this selective reduction process was obtained with the addition of 5 wt. % of reductant and 10 wt. % of sodium sulfate in nickel ore, which was reduced at 1150oC for 60 minutes. It resulted in 4.60% and 73.23% for nickel grade and its recovery, respectively.

Synthesis, characterization and X-ray studies of new chiral five-six-membered ring, [4.3.0] heterobicyclic system of monomeric boronates

2011 ◽  
Vol 696 (11-12) ◽  
pp. 2420-2428 ◽  
Author(s):  
José María Rivera ◽  
Susana Rincón ◽  
Norberto Farfán ◽  
Rosa Santillan
Keyword(s):  
Membered Ring ◽  
X Ray

Bestimmung von innermolekularen Torsionswinkeln aus Hyperfeinstruktur-Aufspaltungen und g-Faktoren

1965 ◽  
Vol 20 (9) ◽  
pp. 1117-1121 ◽  
Author(s):  
K. Möbius
Keyword(s):  
Electron Diffraction ◽  
Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbons ◽  
Small Amplitude ◽  
Membered Ring ◽  
Radical Ions ◽  
Hydrogen Atoms ◽  
Stereochemical Structure ◽  
X Ray ◽  
Phenyl Rings

The stereochemical structure of aromatic hydrocarbons in solution being overcrowded with hydrogen atoms is not known with certainty, because the conventional X-ray and electron diffraction methods are suitable only for samples in the crystalline and vapor phase. Using EPR spectroscopy for the aromatic hydrocarbon radicals biphenyl (—), phenanthrene (—) and pentaphenylcyclopentadienyl (PPCPD) innermolecular twist and bond angles could be determined by means of hfssplittings and g-factors. Stably solvated biphenyl radical ions are found to have twist angles of 38 ±2°; phenanthrene ions turn out to be planar but change their angles of hybridization at particular positions; in the PPCPD radical the phenyl rings oscillate with small amplitude around planes orthogonal to the five-membered ring.

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