Metal hydride mediated reduction of 3-(alkylthio)oxindoles containing other potentially reducible groups

1997 ◽  
Vol 75 (5) ◽  
pp. 536-541 ◽  
Author(s):  
Terrence J. Connolly ◽  
Tony Durst
Keyword(s):  
Benzene Ring ◽  
Metal Hydride ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Ester Group ◽  
Methyl Group ◽  
Mediated Reduction

The reduction of several 3-(methylthio)oxindoles bearing ester groups on the benzene ring has been studied. The reaction is very dependent on the substitution of the oxindole, and the position of the ester group. Deprotonation of the C3 center by the metal hydride is the major initial pathway. This deprotonation plays a role in the reduction of the pendant ester group. Ester groups ortho, and presumably para, to C3 are very difficult to reduce, reaction only occurring with excess LiAlH4 at elevated temperatures. Once reduction starts, it is very difficult to stop, with reduction of the ester to a methyl group being observed. When deprotonation at this center is blocked, ester reduction becomes straightforward and can be accomplished at room temperature with LiEt3BH. Keywords: oxindole, reduction, anion.

Mechanical Properties and Dislocation Structure of Single Crystal Cdte Deformed in Compression at 300°C

1976 ◽  
Vol 34 ◽  
pp. 592-593
Author(s):  
Ernest L. Hall ◽  
J. B. Vander Sande
Keyword(s):  
Mechanical Properties ◽  
Single Crystal ◽  
Dislocation Structure ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Strain Curve ◽  
Optical Devices ◽  
Semiconductor Compound ◽  
Wide Range ◽  
Sample Orientation

The present paper describes research on the mechanical properties and related dislocation structure of CdTe, a II-VI semiconductor compound with a wide range of uses in electrical and optical devices. At room temperature CdTe exhibits little plasticity and at the same time relatively low strength and hardness. The mechanical behavior of CdTe was examined at elevated temperatures with the goal of understanding plastic flow in this material and eventually improving the room temperature properties. Several samples of single crystal CdTe of identical size and crystallographic orientation were deformed in compression at 300°C to various levels of total strain. A resolved shear stress vs. compressive glide strain curve (Figure la) was derived from the results of the tests and the knowledge of the sample orientation.

Spherulite Structures in a Melt Spun Fe-Ni Austenitic Steel

1985 ◽  
Vol 43 ◽  
pp. 52-53
Author(s):  
G. M. Michal ◽  
T. K. Glasgow ◽  
T. J. Moore
Keyword(s):  
Austenitic Steel ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Large Range ◽  
Amorphous Structure ◽  
Nucleation And Growth ◽  
Ni Alloys ◽  
Melt Spun ◽  
Crystal Fibers ◽  
Rapidly Solidified

Large additions of B to Fe-Ni alloys can lead to the formation of an amorphous structure, if the alloy is rapidly cooled from the liquid state to room temperature. Isothermal aging of such structures at elevated temperatures causes crystallization to occur. Commonly such crystallization pro ceeds by the nucleation and growth of spherulites which are spherical crystalline bodies of radiating crystal fibers. Spherulite features were found in the present study in a rapidly solidified alloy that was fully crysstalline as-cast. This alloy was part of a program to develop an austenitic steel for elevated temperature applications by strengthening it with TiB2. The alloy contained a relatively large percentage of B, not to induce an amorphous structure, but only as a consequence of trying to obtain a large volume fracture of TiB2 in the completely processed alloy. The observation of spherulitic features in this alloy is described herein. Utilization of the large range of useful magnifications obtainable in a modern TEM, when a suitably thinned foil is available, was a key element in this analysis.

A Reinvestigation of the Deceptively Simple Reaction of Toluene with ●OH, and the Fate of the Benzyl Radical. I. a Combined Thermodynamic and Kinetic Study on the Competition Between ●OH Addition and Hydrogen Abstraction Reactions.

2019 ◽  
Author(s):  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Marc E. Segovia ◽  
Martina Kieninger ◽  
Oscar Ventura ◽  
...  
Keyword(s):  
Density Functional ◽  
Room Temperature ◽  
Hydrogen Abstraction ◽  
Reaction Rates ◽  
Composite Model ◽  
Alternative Mechanism ◽  
Radical Intermediate ◽  
Experimental Conditions ◽  
Methyl Group ◽  
Benzyl Radical

This work reports density functional and composite model chemistry calculations performed on the reactions of toluene with the hydroxyl radical. Both experimentally observed H-abstraction from the methyl group and possible additions to the phenyl ring were investigated. Reaction enthalpies and heights of the barriers suggest that H-abstraction is more favorable than ●OH addition to the ring. The calculated reaction rates at room temperature and the radical-intermediate product fractions support this view. This is somehow contradictory with the fact that, under most experimental conditions, cresols are observed in a larger concentration than benzaldehyde. Since the accepted mechanism for benzaldehyde formation involves H-abstraction, a contradiction arises that begs for an explanation. In this first part of our work we give the evidences that support the preference of hydrogen abstraction over ●OH addition and suggest an alternative mechanism which shows that cresols can actually arise also from the former reaction and not only from the latter.

A Reinvestigation of the Deceptively Simple Reaction of Toluene with ●OH, and the Fate of the Benzyl Radical. I. a Combined Thermodynamic and Kinetic Study on the Competition Between ●OH Addition and Hydrogen Abstraction Reactions.

2019 ◽  
Author(s):  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Marc E. Segovia ◽  
Martina Kieninger ◽  
Oscar Ventura ◽  
...  
Keyword(s):  
Density Functional ◽  
Room Temperature ◽  
Hydrogen Abstraction ◽  
Reaction Rates ◽  
Composite Model ◽  
Alternative Mechanism ◽  
Radical Intermediate ◽  
Experimental Conditions ◽  
Methyl Group ◽  
Benzyl Radical

This work reports density functional and composite model chemistry calculations performed on the reactions of toluene with the hydroxyl radical. Both experimentally observed H-abstraction from the methyl group and possible additions to the phenyl ring were investigated. Reaction enthalpies and heights of the barriers suggest that H-abstraction is more favorable than ●OH addition to the ring. The calculated reaction rates at room temperature and the radical-intermediate product fractions support this view. This is somehow contradictory with the fact that, under most experimental conditions, cresols are observed in a larger concentration than benzaldehyde. Since the accepted mechanism for benzaldehyde formation involves H-abstraction, a contradiction arises that begs for an explanation. In this first part of our work we give the evidences that support the preference of hydrogen abstraction over ●OH addition and suggest an alternative mechanism which shows that cresols can actually arise also from the former reaction and not only from the latter.

FANSTEEL 85 METAL

Alloy Digest ◽  
1981 ◽  
Vol 30 (6) ◽  
Keyword(s):  
High Temperature ◽  
Physical Properties ◽  
Creep Strength ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Base Alloy ◽  
Heat Treating ◽  
Good Combination ◽  
Bend Strength ◽  
Temperature Performance

Abstract FANSTEEL 85 METAL is a columbium-base alloy characterized by good fabricability at room temperature, good weldability and a good combination of creep strength and oxidation resistance at elevated temperatures. Its applications include missile and rocket components and many other high-temperature parts. This datasheet provides information on composition, physical properties, microstructure, hardness, elasticity, tensile properties, and bend strength as well as creep. It also includes information on low and high temperature performance as well as forming, heat treating, machining, joining, and surface treatment. Filing Code: Cb-7. Producer or source: Fansteel Metallurgical Corporation. Originally published December 1963, revised June 1981.

Strong Coupling: Polariton Bose Condensation

2017 ◽  
Author(s):  
Alexey V. Kavokin ◽  
Jeremy J. Baumberg ◽  
Guillaume Malpuech ◽  
Fabrice P. Laussy
Keyword(s):  
Strong Coupling ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Dissipative System ◽  
Bose Condensation ◽  
Einstein Condensation ◽  
Strong Coupling Regime ◽  
Stimulated Scattering ◽  
Exciton Polaritons ◽  
Bose Einstein

In this Chapter we address the physics of Bose-Einstein condensation and its implications to a driven-dissipative system such as the polariton laser. We discuss the dynamics of exciton-polaritons non-resonantly pumped within a microcavity in the strong coupling regime. It is shown how the stimulated scattering of exciton-polaritons leads to formation of bosonic condensates that may be stable at elevated temperatures, including room temperature.

XXI.—The Synthesis of Some Methyl- and Dimethylfluoranthenes

1972 ◽  
Vol 69 (4) ◽  
pp. 281-286
Author(s):  
H. F. Andrew ◽  
Neil Campbell ◽  
E. M. Swan ◽  
N. H. Wilson
Keyword(s):  
Benzene Ring ◽  
Propionic Acid ◽  
Hydrofluoric Acid ◽  
Phenyl Ring ◽  
Ring Closure ◽  
Methyl Group ◽  
Image Position

3-Methylfluorene-9-propionic acid (1) with hydrofluoric acid undergoes ring-closure on the substituted ring to give 1,2,3,10b-tetrahydro-5-methylfluoranthen-3-one (II).Wolff-Kishner reduction of the ketone yielded l,2,3,10b-tetrahydro-5-methylfluoranthene which on dehydrogenation gave 2-methylfluoranthene (III, R=H) identical with a sample prepared according to the method of Tucker (1952) and differing from 8-methylfluoranthene. This proved that ring-closure of (I) had occurred as expected on the methyl-bearing benzene ring. In this instance ring-closure occurs in the position meta to the methyl group and is reminiscent of the similar ring-closure of 2-phenyl-2-p-tolylpropionic acid to give 6-methyl-3-phenylindanone (Pfeiffer and Roos 1941). It thus provided a further example of the limitations of von Braun's statement that Friedel-Crafts ring-closure occurs much less readily at the position meta to a methyl group than on a phenyl ring (von Braun, Manz and Reinsch 1928).

On the use of Ozawa/Flynn/Wall method to determine aging activation energy for elastomers

2021 ◽  
pp. 009524432110203
Author(s):  
Sudhir Bafna
Keyword(s):  
Mechanical Properties ◽  
Activation Energy ◽  
Weight Loss ◽  
Oxygen Consumption ◽  
Dwell Time ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Degradation Mechanism ◽  
Kinetics Of ◽  
Wall Method

It is often necessary to assess the effect of aging at room temperature over years/decades for hardware containing elastomeric components such as oring seals or shock isolators. In order to determine this effect, accelerated oven aging at elevated temperatures is pursued. When doing so, it is vital that the degradation mechanism still be representative of that prevalent at room temperature. This places an upper limit on the elevated oven temperature, which in turn, increases the dwell time in the oven. As a result, the oven dwell time can run into months, if not years, something that is not realistically feasible due to resource/schedule constraints in industry. Measuring activation energy (Ea) of elastomer aging by test methods such as tensile strength or elongation, compression set, modulus, oxygen consumption, etc. is expensive and time consuming. Use of kinetics of weight loss by ThermoGravimetric Analysis (TGA) using the Ozawa/Flynn/Wall method per ASTM E1641 is an attractive option (especially due to the availability of commercial instrumentation with software to make the required measurements and calculations) and is widely used. There is no fundamental scientific reason why the kinetics of weight loss at elevated temperatures should correlate to the kinetics of loss of mechanical properties over years/decades at room temperature. Ea obtained by high temperature weight loss is almost always significantly higher than that obtained by measurements of mechanical properties or oxygen consumption over extended periods at much lower temperatures. In this paper, data on five different elastomer types (butyl, nitrile, EPDM, polychloroprene and fluorocarbon) are presented to prove that point. Thus, use of Ea determined by weight loss by TGA tends to give unrealistically high values, which in turn, will lead to incorrectly high predictions of storage life at room temperature.

Effects of Elevated Temperatures on the Compressive Strength of HFCC

2011 ◽  
Vol 261-263 ◽  
pp. 416-420 ◽  
Author(s):  
Fu Ping Jia ◽  
Heng Lin Lv ◽  
Yi Bing Sun ◽  
Bu Yu Cao ◽  
Shi Ning Ding
Keyword(s):  
Compressive Strength ◽  
Elevated Temperature ◽  
Fly Ash ◽  
Room Temperature ◽  
Elevated Temperatures ◽  
Relative Strength ◽  
Ordinary Concrete ◽  
Residual Compressive Strength ◽  
Fly Ash Concrete ◽  
The Relationship

This paper presents the results of elevated temperatures on the compressive of high fly ash content concrete (HFCC). The specimens were prepared with three different replacements of cement by fly ash 30%, 40% and 50% by mass and the residual compressive strength was tested after exposure to elevated temperature 250, 450, 550 and 650°C and room temperature respectively. The results showed that the compressive strength apparently decreased with the elevated temperature increased. The presence of fly ash was effective for improvement of the relative strength, which was the ratio of residual compressive strength after exposure to elevated temperature and ordinary concrete. The relative compressive strength of fly ash concrete was higher than those of ordinary concrete. Based on the experiments results, the alternating simulation formula to determine the relationship among relative strength, elevated temperature and fly ash replacement is developed by using regression of results, which provides the theoretical basis for the evaluation and repair of HFCC after elevated temperature.

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