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Cyano substituent effects on enol and enethiol acidity and basicity: The protonation and deprotonation of 3-hydroxy-2-propenenitrile and its thio analogue

The gas-phase basicity and acidity of 3-hydroxy-2-propenenitrile (3-hydroxyacrylonitrile) and its sulfur-containing analogue, 3-mercapto-2-propenenitrile, have been determined by means of high-level G3B3 ab initio calculations and, in the case of the latter compound, compared with the experimental values obtained by means of FT-ICR mass spectrometry techniques, and with previous reported values for the N{triple bond, long}C-CH{double bond, long}CH-X (X = CH3, NH2, SiH3, PH2) analogues. For both compounds the Z-isomer is the dominant species in the gas-phase. Protonation takes place in both cases at the cyano group. The loss of the proton from the substituent, was found to be systematically much more favorable than the deprotonation at the HC{double bond, long}CH group. 3-Hydroxy-2-propenenitrile is predicted to be a stronger base by ca. 5 kJ mol-1 than its thio analogue, but a weaker acid by 26 kJ mol-1. Both compounds are stronger acids than the corresponding unsubstituted vinyl compounds, because cyano substitution stabilizes much more the deprotonated species than the corresponding neutral compound. There is a clear disagreement between our theoretical estimates for both the gas-phase basicity and the gas-phase acidity of 3-mercapto-2-propenenitrile and the corresponding experimental values, which is consistent with its isomerization to yield isothiazole.

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

 

Properties and Exciting Facts About Isothiazole

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Functional analogues of salicylic acid and their use in crop protection

Functional analogues of salicylic acid are able to activate plant defense responses and provide attractive alternatives to conventional biocidal agrochemicals. However, there are many problems that growers must consider during their use in crop protection, including incomplete disease reduction and the fitness cost for plants. High-throughput screening methods of chemical libraries allowed the identification of new compounds that do not affect plant growth, and whose mechanisms of action are based on priming of plant defenses, rather than on their direct activation. Some of these new compounds may also contribute to the discovery of unknown components of the plant immune system.

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

 

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Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Review, the author is Dyachenko, Vladimir D. and a compound is mentioned, Recommanded Product: Isothiazole, Isothiazole, introducing its new discovery. Recommanded Product: Isothiazole

Cyanothioacetamide: A polyfunctional reagent with broad synthetic utility

The review integrates and analyzes the published data on the chemical reactivity of a-cyanothioacetamide, a convenient starting compound for the preparation of activated alkenes, functionally substituted pyrans, thiopyrans, pyridines, thiophenes, pyrroles, quinolines, isoquinolines, pyrimidines, thienopyrroles, pyrazolopyridines, pyridothienopyrimidines and pyrimidothienodiazines. The relatively small a-cyanothioacetamide molecule has several reaction centres. Nucleophilic reactions of the methylene group are covered most extensively, including the Thorpe reaction; reactions with diazonium salts, azides, iso(thio)cyanates and nitroso compounds; nucleopilic substitution; Knoevenagel condensation; Michael reaction; and multicomponent syntheses. Separate parts of the review are devoted to nucleophilic reactions involving the thiocarbonyl and amino groups and electrophilic reactions involving thiocarbonyl and nitrile groups. The focus is on the publications of the last 15 years.

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

 

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Medicinal chemistry perspective of fused isoxazole derivatives

Nitrogen containing heterocyclic rings with an oxygen atom is considered as one of the best combination in medicinal chemistry due to their diversified biological activities. Isoxazole, a five membered heterocyclic azole ring is found in naturally occuring ibetonic acid along with some of the marketed drugs such as valdecoxib, flucloxacillin, cloxacillin, dicloxacillin, and danazol. It is also significant for showing antipsychotic activity in risperidone and anticonvulsant activity in zonisamide, the marketed drugs. This review article covers research articles reported till date covering biological activity along with SAR of fused isoxazole derivatives.

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

 

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Spin-Spin Couplings Between 13C Nuclei in Five-Membered Heteroaromatic Ring Systems

A set of 1J(CC) spin-spin coupling constants are reported for 11 five-membered heteroaromatic molecules, including all relevant diazole, triazole, oxazole, oxadiazole, thiazole and thiadiazole systems.The coupling show a clear distinction between carbon-carbon bonds which are formally double or single, respectively.There seems to be no correlation of the couplings with the bond lengths concerned, in spite of some apparent trends.Potential applications of the couplings are discussed in assessing the aromaticity of five-membered heterocycles. – Keywords: 13C NMR Carbon-carbon coupling constants Heteroaromatic five-membered rings Diazoles Triazoles Oxazoles Oxadiazoles Thiazoles Thiadiazoles

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

 

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Metal-catalyzed direct arylation of 1,2-azoles

Over the last 20 years, there has been significant progress in the direct CH (het)arylation chemistry of a wide variety of (het)arenes. Herein, the application of direct CH arylation on the 1,2-azoles: pyrazoles, isothiazoles, and isoxazoles and their annulated analogues is reviewed starting from the first arylation methods on 1,2-azoles until 2018.

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

 

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PDE7-selective and dual inhibitors: Advances in chemical and biological research

Phosphodiesterase 7 (PDE7) is an intracellular enzyme that specifically hydrolyzes the second messenger, cyclic-3?,5?-adenosine monophosphate (cAMP), into inactive noncyclic nucleotide, 5?-AMP. To date, many structurally diverse compounds with PDE7 inhibitory properties have been described, including selective PDE7 inhibitors, dual PDE4/PDE7, PDE7/PDE8, and PDE7/GSK-3 inhibitors, and non-selective PDE inhibitors with high affinity for PDE7. Inhibitors of PDE7 have provided beneficial effects in animal models of inflammatory and neurological disorders, including Alzheimer?s disease, Parkinson?s disease, multiple sclerosis, and many others. This review is a comprehensive summary of the current state-of-the-art in the field of design and synthesis of PDE7 inhibitors, their physicochemical properties, biological evaluation, and structure-activity relationships as well as it highlights the updated evidence for a potential therapeutic utility of these compounds. Moreover, new approaches to obtain more effective and safer PDE7 inhibitors than those available now are presented.

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

 

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Synthesis and application of stable nitroxide free radicals fused with carbocycles and heterocycles

Stable nitroxide free radicals have traditionally been associated with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) or its 4-substituted derivatives as relatively inexpensive and readily accessible compounds with limited possibilities for further chemical modification. Over the past two decades, there has been a resurgence of interest in stable free radicals with proper functionalization tuned for various applications. The objective of this review is to present recent results with synthetic methodologies to achieve stable nitroxide free radicals fused with aromatic carbocycles and heterocycles. There are two main approaches for accessing stable nitroxide free radicals fused with arenes, e.g., isoin-doline-like nitroxides: further functionalization and oxidation of phthalimide or inventive functionalization of pyrroline nitroxide key compounds. The latter also offers the con-structions of versatile heterocyclic scaffolds (furan, pyrrole, thiophene, 1,2-thiazole, selenophene, pyrazole, pyrimidine, pyridine, pyridazine, 1,5-benzothiazepine) that are fused with pyrroline or tetrahydropyridine nitroxide rings. The possible applications of these new stable nitroxide free radicals, such as covalent spin labels and noncovalent spin probes of proteins and nucleic acids, profluorescent probes, building blocks for construction of dual active drugs and electroactive materials, and substances for controlled free radical polymerization, are discussed.

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

 

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A vascular endothelial growth factor inhibitor compounds (by machine translation)

A vascular endothelial growth factor inhibitor compounds. The invention belongs to the field of medicine, the special formula I salts of the compound. The invention also relates to the method for synthesizing the compounds, in pharmaceutical use and pharmaceutical formulations, particularly with respect to the tumor, the treatment of angiogenesis. (by machine translation)

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

 

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A 15N NMR Study of Some Azoles

15N NMR data are reported for 42 azoles, taken mostly at a standard concentration and in a common solvent (0.5 M dimethyl sulfoxide with a 0.01 M increment of Cr(acac)3 for each nitrogen atom present).Signal assignments were assisted by comparison with 14N line widths, the use of 2J(15N1H) couplings, and shielding calculations obtained by the INDO/S-SOS approach.The generally large differences in nitrogen-shielding changes permitted rather facile shift assignments.

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