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The electronic states of 1,2,5-thiadiazole studied by VUV absorption spectroscopy and ab initio configuration interaction methods

The 1,2,5-thiadiazole VUV absorption spectrum over the range 5-12 eV has been obtained for the first time. It shows broad bands centred near 5.0, 7.2, 7.7, 8.7, 9.6 and 10.6 eV; several of these show well resolved vibrational structure. A number of valence states and Rydberg states relating to the first and second ionisation energies have been identified. The doubling of some bands in the 4.7 eV region (previously reported) is confirmed; a 3s Rydberg state shows a similar phenomenon, which we also attribute to a non-planar upper state; a study of the (planar) equilibrium geometry of the corresponding triplet Rydberg state shows it is a saddle point. Electronic excitation energies for valence (singlet and triplet) and Rydberg-type states have been computed using ab initio multi-reference multi-root CI methods. These studies used a triple-zeta + double polarisation basis set, augmented by diffuse (Rydberg) orbitals. The theoretical study shows the nature of the more intense Rydberg state types, and positions of the main valence and Rydberg bands. There is generally a good correlation between the theoretical intensities and the experimental envelope. Reconsideration of the order of cationic states in the UV-photoelectron spectrum, crucial to the Rydberg state interpretation, has led to the sequence: 2B1 < 2B2 < 2A2 < 2A1. Study of the excitation energies to specific upper states, also supports this order. The value of IE1 is refined to 10.111 eV. Equilibrium structures show the pi- and sigma-cations are planar, in contrast to the lowest triplet state. A reaction mechanism is the microscopic path by which reactants are transformed into products. Each step is an elementary reaction. In my other articles, you can also check out more blogs about 288-16-4 Reference£º
Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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A method for inhibiting VEGF injection of the pharmaceutical composition (by machine translation)

The invention belongs to the field of medicine, in particular to inhibit VEGF of the formula I compound and salt of injection drug composition, in pharmaceutical use and pharmaceutical formulations, particularly with respect to the tumor, the treatment of angiogenesis. The invention also relates to the method for synthesizing the compounds. (by machine translation)

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A vascular endothelial growth factor inhibitors of the dry powder pharmaceutical composition (by machine translation)

The invention relates to the treatment of respiratory diseases especially asthma of a vascular endothelial growth factor inhibitors of the dry powder pharmaceutical composition, in particular to the active compound component I its physiologically acceptable salt, one or several kinds can be used for inhalation pharmaceutical excipient dry powder inhalation pharmaceutical composition. (by machine translation)

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Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Cycloaddttion, ring-opening, and other novel reactions of thiophenes

Synthetically useful reactions of thiophenes arid benzolb]thiophenes are reviewed in which the aromatzcity of the thiophene ring is lost either permanently or temporarilyj i.e. so-called “non-benzenoid” reactions. These include cyclcaddition reactions with arynes, hetarynes, carbenes, nitrsnes, olefins, acetylenes, ketones, and other substrates and various ring-opening reactions, e.g. of organometallic derivatives and 2-Aminothiophenes. Also reviewed are C-2 protonation and reactions of thiophenes at the sulprtur atom, e.g. alkylation. Brief reference is made to thiophene I, l-dioxideu and attention is drawn to other littie-used reactions of thiophenes of potential synthetic usefulness, e.g. inverted reactivity of thienyl-lithium compounds.

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Reference£º
Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Survey of main group compounds (hbr) at the gaussian-4 level of theory: Adiabatic ionization energies and enthalpies of formation

Gas phase adiabatic ionization energies (AIEs) and standard state (298.15. K, 1. atm) enthalpies of formation DeltafH(g) were calculated at the Gaussian-4 (G4) level of theory for a suite of 319 and 398 main group compounds, respectively, containing the elements hydrogen through bromine. National Institute of Standards and Technology (NIST) evaluated AIEs were available for comparison with 44 compounds, yielding good agreement when the significant variability among the individual experimental reports was taken into consideration. AIEs were estimated at the G4 level of theory for a further 126 main group compounds having at least one experimental datapoint in the NIST database, but not a NIST evaluated AIE, as well as 149 main group compounds without any experimental data in the NIST database. Experimental DeltafH(g) were available for comparison with 144 compounds, yielding good agreement, particularly against compounds with evaluated DeltafH(g) DeltafH(g) were estimated at the G4 level of theory for a further 254 main group compounds without any experimental data. The datasets comprise a benchmark set of theoretical data against which to assess future experimental and theoretical results.

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Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Five-Membered Ring Systems: With N and S Atom

This review chapter describes the syntheses and reactions of these 5-membered heterocyclic ring systems containing nitrogen and sulfur (reported during 2018). The importance of these p-rich heterocycles in medicinal chemistry and natural products is also covered.

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Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Carboxylation of C-H bonds using N -heterocyclic carbene gold(I) complexes

A highly efficient [(NHC)AuI]-based (NHC = N-heterocyclic carbene) catalytic system for the carboxylation of aromatic and heteroaromatic C-H bonds was developed. The significant base strength of the Au-OH species is at the origin of the activation process and permits the facile functionalization of C-H bonds without the use of other organometallic reagents.

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Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Antipoliovirus activity and mechanism of action of 3-methylthio-5-phenyl-4-isothiazolecarbonitrile

Our previous studies described the synthesis and the antiviral activity of 3,4,5-trisubstituted isothiazole derivatives that were found to be particularly effective against enteroviruses. Compound 3-methylthio-5-phenyl-4-isothiazolecarbonitrile (IS-2) exhibited an interesting anti-poliovirus activity with a high selectivity index. In the present study we investigated the mechanism of action of this compound. Studies on the time of IS-2 addition to poliovirus type 1 infected cells suggested that the compound may inhibit some early process of viral replication. In order to determine its mechanism of action, we evaluated the rate of attachment and internalization of purified [3H]uridine-labeled poliovirus to HEp-2 cells in the presence or absence of IS-2. No effect on poliovirus adsorption and internalization to host cells was detected. We also investigated the influence of the compound on virus uncoating using labeled poliovirus and measuring the radioactivity of oligoribonucleotides formed from viral RNA susceptible to ribonuclease. These experiments demonstrated that poliovirus uncoating is influenced by IS-2 action.

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Reference£º
Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Heteroarylmethylbenzenes

Compounds of formula I STR1 wherein Z is thiazolyl or isothiazolyl, and X, R, R0, R1, R2 and R3 are as defined in the description, have valuable pharmaceutical properties and are effective especially against tumors.

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Reference£º
Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com

 

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Time-Resolved Photoelectron Studies of Thiophene and 2,5-Dimethylthiophene

The photoinduced dynamics of thiophene and 2,5-dimethylthiophene (2,5-DMT) were investigated upon excitation at 200 and 255 nm (2,5-DMT only) using time-resolved photoelectron spectroscopy and compared with results from ab initio coupled cluster calculations. For thiophene, depopulation of the initially excited B2(pi3pi4?) state to the lower-lying A1(pi2pi4?) state occurs within 25 ¡À 20 fs, with a subsequent bifurcation into a ring-puckering channel and a ring-opening channel with lifetimes of 80 ¡À 20 and 450 ¡À 50 fs, respectively. For 2,5-DMT, the dynamics following excitation at 200 nm is described by a monoexponential decay with a time constant of 120 ¡À 20 fs, while that following excitation at 255 nm is best fit by a biexponential decay with time constants of 115 ¡À 20 fs and 15 ¡À 3 ps, respectively. The fast signal observed after excitation of 2,5-DMT is assigned to the ring-opening channel, which is favored with respect to thiophene due to a lower excited-state barrier along the ring-opening coordinate and an increased inertia toward the ring-puckering channel. Coupled cluster calculations have been undertaken to compare the relaxation dynamics of thiophene to thiazole and isothiazole. For the latter two molecules, we find a strong gradient along the ring-opening coordinate in the Franck-Condon region of the initially populated pipi? state and predict that ring-opening is the dominating relaxation channel after photoexcitation. We use the extracted information for a comparison of the thiophene dynamics with the light-induced processes observed in other five-membered heterocyclic molecules.

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Reference£º
Isothiazole – Wikipedia,
Isothiazole – ScienceDirect.com