2‐Pyrazolin‐5‐One‐Based Heterocycles: Synthesis and Characterization

A novel series of pyrazoline and thiazole derivatives incorporating 2‐pyrazolin‐5‐one moiety were synthesized starting from α,β‐unsaturated ketones under the effect of hydrazine derivatives and thiosemicarbazide. The obtained pyrazolines 4a , 4b were treated with different reagents to afford N‐substituted pyrazolines 5a , 5b , 6a , 6b , 7a , 7b , 8a , 8b . N‐Thiocarbamoyl pyrazolines 12a , 12b were cyclized using phenacyl bromide, 2,3‐dichloroquinoxaline, and monochloroacetic acid afforded the novel pyrazolinyl thiazoles 13a , 13b , 14a , 14b , 15a , 15b , 16a , 16b , 16c , 16d , 16e , 16f . The newly synthesized compounds were characterized by analytical and spectral data.     

Validation of numerical solvers for liquid metal flow in a complex geometry in the presence of a strong magnetic field

Following the magnetohydrodynamic (MHD) code validation and verification proposal by Smolentsev et al. (Fusion Eng Des 100:65–72, 2015), we perform code to code and code to experiment comparisons between two computational solvers, FLUIDYN and HIMAG, which are presently considered as two of the prospective CFD tools for fusion blanket applications. In such applications, an electrically conducting breeder/coolant circulates in the blanket ducts in the presence of a strong plasma-confining magnetic field at high Hartmann numbers, \(\textit{Ha}\) (\(\textit{Ha}^2\) is the ratio between electromagnetic and viscous forces) and high interaction parameters, \(\textit{N}\) (\(\textit{N}\) is the ratio of electromagnetic to inertial forces). The main objective of this paper is to provide the scientific and engineering community with common references to assist fusion researchers in the selection of adequate computational means to be used for blanket design and analysis. As an initial validation case, the two codes are applied to the classic problem of a laminar fully developed MHD flows in a rectangular duct. Both codes demonstrate a very good agreement with the analytical solution for \(\textit{Ha}\) up to 15, 000. To address the capabilities of the two codes to properly resolve complex geometry flows, we consider a case of three-dimensional developing MHD flow in a geometry comprising of a series of interconnected electrically conducting rectangular ducts. The computed electric potential distributions for two flows (Case A) \(\textit{Ha}=515\), \(\textit{N}=3.2\) and (Case B) \(\textit{Ha}=2059\), \(\textit{N}=63.8\) are in very good agreement with the experimental data, while the comparisons for the MHD pressure drop are still unsatisfactory. To better interpret the observed differences, the obtained numerical data are analyzed against earlier theoretical and experimental studies for flows that involve changes in the relative orientation between the flow and the magnetic field.     

Syntheses and reactions of some fluorinated dienes,cyclobutenes and furans

There are many reports¹ of the pyrolysis of fluorinated organic compounds, including the defluorination of cyclic fluorocarbons over iron to give aromatic compounds. Extending this technique we have investigated the flow pyrolysis of some readily accessible unsaturated fluorocarbons, such as I, II, and III, and found these to be synthetically

useful routes to fluorinated dienes, cyclobutenes, and furans. Pyrolyses were carried out using a nitrogen flow over platinum, iron or caesium fluoride heated at 430–700°. The various products can all be rationalized in terms of intermediate allylic radicals, and the solid substrate influences which allylic radicals are formed.We are also investigating the chemistry of those now accessible compounds, such as IV, V, and VI, and some of the preliminary results are described.

For example the fluoride ion induced dimerisation of IV gave two major products VII and VIII via a particular interesting mechanism.

     

Diverse reactivity of α‐carbanions derived from alkylidenephosphoranes toward 2‐(1λ5‐diazynylidene)‐1H‐indene‐1,3‐(2H)dione. General approach to conjugated oxadiazines,pyridazines and spiro[3]pyrazoles

Different types of phosphonium carbanions were applied to 2‐diazonio‐1,3‐dioxo‐2,3‐dihydro‐1H‐inden‐2‐ide ( 1 ) in order to synthesize a number of condensed and fused N‐heterocycles. When 1 was treated with cyanomethyltriphenylphosphonium chloride oxadiazine‐, and pyridazine derivatives were obtained whereas bis‐indanylidene derivatives resulted from the reaction of 1 with methyl_ and ethyltriphenylphosphonium bromides. On the other hand, a series of substituted and unsubstituted spiro[3′]pyrazoles were obtained from the di azo substrate when reacted with vinyl_and allyltriphenylphosphonium bromides.     

Synthesis and X-ray structures of dinuclear and trinuclear gold(I) and dinuclear gold(II) amidinate complexes

The structures of the trinuclear gold(I), [Au(3)(2,6-Me(2)-form)(2)-(THT)Cl], the dinuclear [Au(2)(2,6-Me(2)-form)(2)], and the oxidative-addition product [Au(2)(2,6-Me(2)-form)(2)Cl(2)] formamidinate complexes are reported. The trinuclear complex is stable with gold-gold distances 3.01 and 3.55 A. The gold-gold distance in the dinuclear complex decreases upon oxidative-addition with halogens from 2.7 to 2.5 A, similar to observations made with the dithiolates and ylides.     

ChemInform Abstract: The Ground-State Potential Energy Surface of Diazene

has been studied by using a complete active space MCSCF wave function generated by distributing eight electrons among eight orbitals.     

Synthesis of 2,3-dihydro-1,3,4-thiadiazole,thiazole, and triazolo[4,3-a]pyrimidine derivatives from ethyl benzoylacetate

Thiophene and thiazole derivatives can be obtained from potassium salt of ethyl 3-oxo-3-phenyl-2-[(phenylamino)thioxomethyl]propanoate and ethyl chloroacetate in N,N-dimethylformamide solution under different conditions. 2,3-Dihydro-1,3,4-thiadiazoles and triazolo[4,3-a]pyrimidine were obtained from reaction of hydrazonoyl halides with each of thioanilide and pyrimidine-2-thione, respectively. Structures of the newly synthesized compounds were elucidated on the basis of elemental analysis, spectral data, and alternative synthesis route whenever possible. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:107–113, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10222     

Organophosphorus chemistry 23 [1], the reaction of α,β-unsaturated nitriles with alkyl phosphites and phosphorus ylides

Wittig reagents 2 react with furfurylidenemalonitrile ( 1a ) and thienylidenemalonitrile ( 1b ) to give a mixture of products ( 6 and 7 ). Compound 1b reacts with di-alkyl phosphites ( 3 ) and trialkyl phosphites ( 4 ) to give the phosphonate 1:1 adducts 9 and 12 , respectively. Structures of the new products were confirmed on the basis of elemental analyses and spectral studies.