Photochemical and thermal rearrangements of some 3H-pyrazoles

1979 ◽  
Vol 57 (10) ◽  
pp. 1186-1200 ◽  
Author(s):  
William J. Leigh ◽  
Donald R. Arnold

Low temperature (−70 °C) irradiation of 3,3,4,5-tetramethyl-3H-pyrazole (2a) leads to the formation of the 1,2-diazabicyclo[2.1.0]pent-2-ene (3a), as has been reported previously. Irradiation of 3,3-dimethyl-4,5-diphenyl-3H-pyrazole (2b) under identical conditions did not result in formation of the analogous product but lead instead to formation of the cyclopropene via decomposition of the vinyl diazo compound. The thermal rearrangements of 2a and a series of 5-aryl-3,3-dimethyl-4-phenyl-3H-pyrazoles (2b–d) lead to formation of the 4H-pyrazoles 6a–d and the N-methylpyrazoles 5a–d, resulting from competitive methyl migrations to carbon and nitrogen. The Arrhenius parameters for the rearrangement of 2b were determined. Decomposition of the methiodides derived from the 4H-pyrazoles 6a–d leads to formation of the N-methylpyrazoJes 5a–d; the mechanism of this decomposition was examined by high temperature 1Hmr spectroscopy. The N-methylpyrazoles were synthesized by independent routes and the structures were assigned with the aid of lanthanide shift reagents, 1Hmr solvent shift studies, and 13Cmr spectroscopy. The thermodynamic equilibria of the isomeric N-methylpyrazoles were determined and found to be influenced by a small substituent effect. The photochemical and thermal behaviour of 3H-pyrazoles is discussed and compared to that of 1-pyrazolines.

Author(s):  
P.P.K. Smith

Grains of pigeonite, a calcium-poor silicate mineral of the pyroxene group, from the Whin Sill dolerite have been ion-thinned and examined by TEM. The pigeonite is strongly zoned chemically from the composition Wo8En64FS28 in the core to Wo13En34FS53 at the rim. Two phase transformations have occurred during the cooling of this pigeonite:- exsolution of augite, a more calcic pyroxene, and inversion of the pigeonite from the high- temperature C face-centred form to the low-temperature primitive form, with the formation of antiphase boundaries (APB's). Different sequences of these exsolution and inversion reactions, together with different nucleation mechanisms of the augite, have created three distinct microstructures depending on the position in the grain.In the core of the grains small platelets of augite about 0.02μm thick have farmed parallel to the (001) plane (Fig. 1). These are thought to have exsolved by homogeneous nucleation. Subsequently the inversion of the pigeonite has led to the creation of APB's.


2020 ◽  
Vol 10 (10) ◽  
pp. 59-67
Author(s):  
Victor N. ANTIPOV ◽  
◽  
Andrey D. GROZOV ◽  
Anna V. IVANOVA ◽  
◽  
...  

The overall dimensions and mass of wind power units with capacities larger than 10 MW can be improved and their cost can be decreased by developing and constructing superconducting synchronous generators. The article analyzes foreign conceptual designs of superconducting synchronous generators based on different principles: with the use of high- and low-temperature superconductivity, fully superconducting or only with a superconducting excitation system, and with the use of different materials (MgB2, Bi2223, YBCO). A high cost of superconducting materials is the main factor impeding commercial application of superconducting generators. In view of the state of the art in the technology for manufacturing superconductors and their cost, a conclusion is drawn, according to which a synchronous gearless superconducting wind generator with a capacity of 10 MW with the field winding made of a high-temperature superconducting material (MgB2, Bi-2223 or YBCO) with the «ferromagnetic stator — ferromagnetic rotor» topology, with the stator diameter equal to 7—9 m, and with the number of poles equal to 32—40 has prospects for its practical use in the nearest future.


Alloy Digest ◽  
1980 ◽  
Vol 29 (12) ◽  

Abstract SOMERS LTA Copper is a wrought copper foil that can be annealed at 350 F in 15 minutes to the full-soft condition; its use simplifies the manufacture of printed circuits (LTA = Low-Temperature Annealable). LTA Copper is especially useful for foil weights up to and including one ounce per square foot (0.0014-inch thick) for laminating to high-temperature dielectric substrates. This datasheet provides information on composition, physical properties, and elasticity as well as fatigue. It also includes information on forming, heat treating, and machining. Filing Code: Cu-407. Producer or source: Olin Corporation.


Alloy Digest ◽  
1958 ◽  
Vol 7 (2) ◽  

Abstract CHRO-MOW is a tough hot work steel which will harden from a relatively low temperature in air. It possesses a desirable combination of toughness and red-hardness. This datasheet provides information on composition, physical properties, hardness, and tensile properties. It also includes information on high temperature performance as well as forming, heat treating, and machining. Filing Code: TS-67. Producer or source: Crucible Steel Company of America.


Alloy Digest ◽  
1960 ◽  
Vol 9 (3) ◽  

Abstract NICLOY 5 is a low carbon, nickel ferritic steel reecommended for low temperature service. This datasheet provides information on composition, physical properties, hardness, elasticity, and tensile properties as well as fracture toughness. It also includes information on low and high temperature performance, and corrosion resistance as well as forming, heat treating, machining, and joining. Filing Code: SA-96. Producer or source: Babcock & Wilcox Company.


1961 ◽  
Vol 5 ◽  
pp. 276-284
Author(s):  
E. L. Moore ◽  
J. S. Metcalf

AbstractHigh-temperature X-ray diffraction techniques were employed to study the condensation reactions which occur when sodium orthophosphates are heated to 380°C. Crystalline Na4P2O7 and an amorphous phase were formed first from an equimolar mixture of Na2HPO4·NaH2PO4 and Na2HPO4 at temperatures above 150°C. Further heating resulted in the formation of Na5P3O10-I (high-temperature form) at the expense of the crystalline Na4P4O7 and amorphous phase. Crystalline Na5P3O10-II (low-temperature form) appears after Na5P3O10-I.Conditions which affect the yield of crystalline Na4P2O7 and amorphous phase as intermediates and their effect on the yield of Na5P3O10 are also presented.


2019 ◽  
Vol 32 (1) ◽  
pp. 143-151 ◽  
Author(s):  
Luma Rayane de Lima Nunes ◽  
Paloma Rayane Pinheiro ◽  
Charles Lobo Pinheiro ◽  
Kelly Andressa Peres Lima ◽  
Alek Sandro Dutra

ABSTRACT Salinity is prejudicial to plant development, causing different types of damage to species, or even between genotypes of the same species, with the effects being aggravated when combined with other types of stress, such as heat stress. The aim of this study was to evaluate the tolerance of cowpea genotypes (Vigna unguiculata L. Walp.) to salt stress at different temperatures. Seeds of the Pujante, Epace 10 and Marataoã genotypes were placed on paper rolls (Germitest®) moistened with different salt concentrations of 0.0 (control), 1.5, 3.0, 4.5 and 6.0 dS m-1, and placed in a germination chamber (BOD) at temperatures of 20, 25, 30 and 35°C. The experiment was conducted in a completely randomised design, in a 3 × 4 × 5 scheme of subdivided plots, with four replications per treatment. The variables under analysis were germination percentage, first germination count, shoot and root length, and total seedling dry weight. At temperatures of 30 and 35°C, increases in the salt concentration were more damaging to germination in the Epace 10 and Pujante genotypes, while for the Marataoã genotype, damage occurred at the temperature of 20°C. At 25°C, germination and vigour in the genotypes were higher, with the Pujante genotype proving to be more tolerant to salt stress, whereas Epace 10 and Marataoã were more tolerant to high temperatures. Germination in the cowpea genotypes was more sensitive to salt stress when subjected to heat stress caused by the low temperature of 20°C or high temperature of 35°C.


2006 ◽  
Vol 527-529 ◽  
pp. 999-1002
Author(s):  
Junji Senzaki ◽  
Atsushi Shimozato ◽  
Kenji Fukuda

Low-temperature post-oxidation annealing (POA) process of high-reliability thermal oxides grown on 4H-SiC using new apparatus that generates atomic hydrogen radicals by high-temperature catalyzer has been investigated. Atomic hydrogen radicals were generated by thermal decomposition of H2 gas at the catalyzer surface heated at high temperature of 1800°C, and then exposed to the sample at 500°C in reactor pressure of 20 Pa. The mode and maximum values of field-to-breakdown are 11.0 and 11.2 MV/cm, respectively, for the atomic hydrogen radical exposed sample. In addition, the charge-to-breakdown at 63% cumulative failure of the thermal oxides for atomic hydrogen radical exposed sample was 0.51 C/cm2, which was higher than that annealed at 800°C in hydrogen atmosphere (0.39 C/cm2). Consequently, the atomic hydrogen radical exposure at 500°C has remarkably improved the reliability of thermal oxides on 4H-SiC wafer, and is the same effect with high-temperature hydrogen POA at 800°C.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Fan Liu ◽  
Hua Li ◽  
Junwei Wu ◽  
Bin Wang ◽  
Na Tian ◽  
...  

AbstractThe LOX genes have been identified and characterized in many plant species, but studies on the banana LOX genes are very limited. In this study, we respectively identified 18 MaLOX, 11 MbLOX, and 12 MiLOX genes from the Musa acuminata, M. balbisiana and M. itinerans genome data, investigated their gene structures and characterized the physicochemical properties of their encoded proteins. Banana LOXs showed a preference for using and ending with G/C and their encoded proteins can be classified into 9-LOX, Type I 13-LOX and Type II 13-LOX subfamilies. The expansion of the MaLOXs might result from the combined actions of genome-wide, tandem, and segmental duplications. However, tandem and segmental duplications contribute to the expansion of MbLOXs. Transcriptome data based gene expression analysis showed that MaLOX1, 4, and 7 were highly expressed in fruit and their expression levels were significantly regulated by ethylene. And 11, 12 and 7 MaLOXs were found to be low temperature-, high temperature-, and Fusarium oxysporum f. sp. Cubense tropical race 4 (FocTR4)-responsive, respectively. MaLOX8, 9 and 13 are responsive to all the three stresses, MaLOX4 and MaLOX12 are high temperature- and FocTR4-responsive; MaLOX6 and MaLOX17 are significantly induced by low temperature and FocTR4; and the expression of MaLOX7 and MaLOX16 are only affected by high temperature. Quantitative real-time PCR (qRT-PCR) analysis revealed that the expression levels of several MaLOXs are regulated by MeJA and FocTR4, indicating that they can increase the resistance of banana by regulating the JA pathway. Additionally, the weighted gene co-expression network analysis (WGCNA) of MaLOXs revealed 3 models respectively for 5 (MaLOX7-11), 3 (MaLOX6, 13, and 17), and 1 (MaLOX12) MaLOX genes. Our findings can provide valuable information for the characterization, evolution, diversity and functionality of MaLOX, MbLOX and MiLOX genes and are helpful for understanding the roles of LOXs in banana growth and development and adaptations to different stresses.


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