September 6,2021 News Discover the magic of the 130-03-0

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The kinetics of the hydronium-ion catalysed hydrolysis of the following heterocyclic methyl enol ethers have been measured: 3-methoxybenzofuran, 3-methoxybenzothiophene, 3-methoxyindole, 3-methoxy-1-methylindole, 3-methoxyfuran, 3-methoxythiophene, and 2-methoxythiophene.On the basis of the solvent isotope effect kH/kD = 3.08 and the failure to detect deuterium exchange when the solvent was CD3CN:D2O (9:1 v/v) it was concluded that the rate limiting step in the hydrolysis of 3-methoxybenzofuran is C-protonation.The effect of the ring-oxygen atom was measured by comparing the rate of hydrolysis of 3-methoxybenzofuran with that of 3-methoxyindene which occurs 2100 times faster.In contrast to the behaviour of 3-methoxybenzofuran the isotope effects, kH/kD, for the hydrolyses of 3-methoxyfuran, 3-methoxythiophene, 3-methoxyindole, 3-methoxy-1-methylindole and 2-methoxythiophene are ca 0.4 – 0.5 and deuterium exchange is much faster than hydrolysis when the solvent is CD3CN:D2O (9:1 v/v).It was therefore concluded that with these compound C-protonation is rapid and reversible and that slow step is attack by water on the intermediate cation.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

September 3,2021 News Archives for Chemistry Experiments of 130-03-0

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Controlling the internal motions of molecules by outside stimuli is a decisive task for the generation of responsive and complex molecular behavior and functionality. Light-induced structural changes of photoswitches are of special high interest due to the ease of signal application and high repeatability. Typically photoswitches use one reaction coordinate in their switching process and change between two more or less-defined states. Here we report on new twisted hemithioindigo photoswitches enabling two different reaction coordinates to be used for the switching process. Depending on the polarity of the solvent, either complete single bond (in DMSO) or double bond (in cyclohexane) rotation can be induced by visible light. This mutually independent switching establishes an unprecedented two-dimensional control of intramolecular rotations in this class of photoswitches. The mechanistic explanation involves formation of highly polar twisted intramolecular charge-transfer species in the excited state and is based on a large body of experimental quantifications, most notably ultrafast spectroscopy and quantum yield measurements in solvents of different polarity. The concept of pre-twisting in the ground state to open new, independent reaction coordinates in the excited state should be transferable to other photoswitching systems.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

September 1,2021 News Properties and Exciting Facts About 130-03-0

Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.Read on for other articles about 130-03-0

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Hemithioindigo (HTI) photoswitches have a tremendous potential for biological and supramolecular applications due to their absorptions in the visible-light region in conjunction with ultrafast photoisomerization and high thermal bistability. Rational tailoring of the photophysical properties for a specific application is the key to exploit the full potential of HTIs as photoswitching tools. Herein we use time-resolved absorption spectroscopy and Hammett analysis to discover an unexpected principal limit to the photoisomerization rate for donor-substituted HTIs. By using stationary absorption and fluorescence measurements in combination with theoretical investigations, we offer a detailed mechanistic explanation for the observed rate limit. An alternative way of approaching and possibly even exceeding the maximum rate by multiple donor substitution is demonstrated, which give access to the fastest HTI photoswitch reported to date. An unexpected principal limit to the photoisomerization rate for donor-substituted hemithioindigos (HTIs; see figure) has been discovered; this provides a quantitative estimate for the highest possible photoisomerization rate. A mechanistic explanation for the observed limit is offered together with an alternative way of approaching the maximum rate by multiple donor substitution. This approach gave access to the fastest HTI photoswitch reported to date.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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A short and efficient synthesis of condensed 1,4-oxathiin-2-ones from easily available phenols is described. The key step in this synthesis is a hitherto unreported anionic rearrangement under directed metalation conditions. The rearrangement occurs after side chain deprotonation of a methyl sulfanyl group by an O-carbamate directed metalating group and the reaction mixture is kept at room temperature for 8-12 h. Acid-mediated cyclisation of the rearranged product affords [1,4]oxathiin-2-one.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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Chemoselective synthesis of thioaurones or 3-hydroxy benzo[b]thiophen-2- aryl ketones, 1-hydroxy naphtho[2,1-b]thiophen-2-aryl ketones and chalcones from N,N-diethyl-ortho-methyl sulfanyl aryl amides were described. (Benzo[b]thiophen-2-yl) alkylates and (naphtho[2,1-b]thiophen-2-yl) alkylates undergo a novel anionic ortho-Fries rearrangement leading to (3-hydroxy benzo[b]thiophen-2-yl) and (1-hydroxy naphtho[2,1-b]thiophen-2-yl) alkyl ketones. The hydroxy ketones were used as intermediates in the synthesis of wide range of benzothienopyranones and thiafluorenones.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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A series of achiral 3-heteroaryl substituted quinuclidin-2-ene derivatives and related compounds have been synthesized by facile methods. The compounds were evaluated for muscarinic and antimuscarinic properties in receptor binding studies using (-)-[3H]-QNB as the radioligand and in a functional assay using isolated guinea pig urinary bladder. 3-(2-Benzofuranyl)-quinuclidin-2-ene (15) displayed the highest M1-receptor affinity in the present series (K(i) = 9.6 nM).

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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Piperidine compounds having the general formula (I), STR1 wherein R 1 is a group having general formula (II), STR2 wherein X is CHR 10, O, S, SO, SO 2 or NR 10, Z 1 is CH 2, O, or S; Z 2 and Z 3 are independently (CH 2) n, n being 0 or 1, O or S or Z 1 and Z 2 may together represent a group –CH CH–; or when Z 3 is (CH 2) n wherein n is 0, Z 1 and Z 2 may together represent a 3-membered divalent group; show potent sigma receptor activity. Furthermore they show effect in animal models indicative of anxiolytic properties. Accordingly they are useful as medicines for the treatment of anxiety, psychosis, epilepsy, convulsion, movement disorders, motor disturbances, amnesia, cerebrovascular diseases, senile demential of the Alzheimer type or Parkinson”s disease.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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(Chemical Equation Presented) A systematic investigation of the reductive ring-expansion reaction of cyclic ketoximes fused to aromatic ringswith diisobutylaluminum hydride (DIBALH) is described. This reaction regioselectively afforded a variety of five- to eight-membered bicyclic heterocycles or tricyclic heterocycles containing nitrogen neighboring an aromatic ring, including indoline, 1,2,3,4,5,6-hexahydrobenz[b]azocine, 3,4-dihydro-2H-benzo[b] [1,4]oxazine, 2,3,4,5-tetrahydrobenzo[b][1,4]thiazepine, 1,2,3,4,5,6- hexahydroazepino[3,2-b]-indole, 2,3,4,5-tetrahydro-1H-benzothieno[2,3-b]azepine, 2,3,4,5-tetrahydro-1H-benzothieno[3,2-b]-azepine, 5,6-dihydrophenanthridine, and 5,6,11,12-tetrahydrodibenz[b, f]azocine. The reaction mechanism leading to the rearrangement was investigated on the basis of the restricted Becke three-parameter plus Lee-Yang-Parr (B3LYP) density functional theory (DFT) with the 6-31G (d) basis set. It was found that the reaction proceeds through a three-centered transition state via a stepwise mechanism because the potential energy curve along the intrinsic reaction coordinate (IRC) had twomaxima (saddle points; TS1 and TS2) and the partial phenonium cation intermediate C. In addition to cyclic ketoximes fused to aromatic rings, the reactions of various cyclic and acyclic ketoximeswere examined to investigate preference of migrating group. It was found that themore electron-rich group migrated preferentially to give the corresponding secondary amines.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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The unstable enolic tautomers 3-hydroxyfuran, 2- and 3-hydroxy-thiophene, 3-hydroxy-pyrrole, 3-hydroxy-1-methyl-pyrrole and their benzo-derivatives have been generated in solution and the rate and equilibrium constants for their ketoization determined.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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The reaction of 1-benzothiophen-3(2H)-one hydrazone with various ketones under different conditions has been studied and a convenient method has been proposed for the synthesis of thienopyrrole derivatives. The method is applicable to the preparation of 1H- and 3H-benzothienopyrroles with a range of substituents. Georg Thieme Verlag Stuttgart.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem