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EFFECT OF ANNELATION ISOMERISM ON OPTICAL PROPERTIES OF SOME THIONAPHTHENE DERIVATIVES. PART II. alpha-(2-THIONAPHTHENYLMERCAPTO)-PROPIONIC ACIDS AND SOME OF THEIR DERIVATIVES

The synthesis and principal properties of alpha-(2-thionaphthenylmercapto)-propionic acids as well as of some of their derivatives have been described.Racemic acid was resolved by crystallization of its diastereometric salts with optically active bases.The asymmetric transformation of laevorotatory alpha-bromopropionic acid to delta(+)alpha-(2-thionaphthenylmercapto)-propionic acid was carried out.The absolute configurations of the enantiomers were elucidated.Optical rotatory dispersion of the laevorotatory enantiomer and its p-bromophenacyl and p-phenylphenacyl esters in the region 365Safety of Benzo[b]thiophen-3(2H)-one

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Continuous-flow synthesis of functionalized phenols by aerobic oxidation of grignard reagents

Phenols are important compounds in chemical industry. An economical and green approach to phenol preparation by the direct oxidation of aryl Grignard reagents using compressed air in continuous gas-liquid segmented flow systems is described. The process tolerates a broad range of functional groups, including oxidation-sensitive functionalities such as alkenes, amines, and thioethers. By integrating a benzyne-mediated in-line generation of arylmagnesium intermediates with the aerobic oxidation, a facile three-step, one-flow process, capable of preparing 2-functionalized phenols in a modular fashion, is established. Putting on airs: Aerobic oxidation of (hetero)aryl Grignard reagents using compressed air proceeds with a gas-liquid continuous-flow system, thus enabling preparation of fucntionalized phenols. By integrating an in-line generation of ArMgBr intermediates with the aerobic oxidation, ortho-functionalized phenols can be assembled. The method demonstrates good functional-group (FG) compatibility, mild reaction conditions, and short reaction times.

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COMPOUNDS AS MODULATORS OF ROR GAMMA

The present invention encompasses compounds of the formula (I) wherein the variables are defined herein which are suitable for the modulation of RORgamma and the treatment of diseases related to the modulation of RORgamma. The present invention also encompasses processes of making compounds of formula (I) and pharmaceutical preparations containing them.

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Regiospecific synthesis of unsubstituted basic skeletons of heterocycles containing nitrogen neighboring an aromatic ring by the reductive ring expansion reaction using diisobutylaluminum hydride

A systematic investigation of reductive ring expansion reaction of oximes with diisobutylaluminum hydride (DIBAH) was performed. The reaction regiospecifically provided a variety of unsubstituted bicyclic heterocycles 3a-3g or tricyclic heterocycles 3h, 3j-3l that contained nitrogen attached to an aromatic ring.

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Synthese d’analogues biheterocycliques du phenanthrene: les methyl-1-<1>benzothieno, benzoseleno<2,3-b>pyrroles, et methyl-1-<1>benzofuro, benzothieno et benzoseleno<3,2-b>pyrroles

The condensation of ethyl sarcosinate on 2- or 3-halogeno 3- or 2-formyl<1>benzofuran, benzothiophene or benzoselenophene, and on the related 2H-<1>-3-benzoheterocyclanones is described.In the last instances the resulting compounds were formylated in the 2-position with subsequent cyclodehydration.After hydrolysis and decarboxylation, the 1-methyl<1>benzothieno-, benzoseleno<2,3-b>pyrroles and the 1-methyl<1>benzofuro, benzothieno- and benzoseleno<3,2-b>pyrroles were thus obtained.

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Application of directed metalation in synthesis. Part 8: Interesting example of chemoselectivity in the synthesis of thioaurones and hydroxy ketones and a novel anionic ortho-Fries rearrangement used as a tool in the synthesis of thienopyranones and thiafluorenones

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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Palladium-catalyzed coupling reaction of 3-bromo benzo[b]furan, -thiophene and -selenophene 2-carboxaldehyde. Preparation of tetracyclic heteroaromatic derivatives

3-Oxo-2,3-dihydrobenzo[b]furans, -thiophenes and -selenophenes 1a-c afforded the bromo-aldehydes 2 under Vilsmeier-Haack-Arnold conditions. Palladium-catalysed aryl-aryl coupling of 2 with o-formyl-phenylboronic acid allowed the formation of dialdehydes 3 which underwent McMurry cyclisation or pinacol condensation to yield polycyclic aromatic derivatives 4 or the dihydroxylated compounds 5.

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A CONVENIENT GENERAL ACCESS TO alpha-SULFENYLATED ACETOPHENONES AND ALKANONES

Friedel-Crafts acylation of arenes with methylthio- (1) or phenylthio-acetyl chloride (2) provides ready access to alpha-methylthio- or alpha-phenylthio-substituted acetophenones.The acyl chlorides 1 and 2 reacted also with organoaluminium reagents to give alpha-sulfenylated alkanones.

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Orange-Red Fluorescent (Partially Rigidified) Donor-pi-(rigidified)-Acceptor System ? Computational Studies

D-pi-A chromophore derived coumarins are studied using ?DFT and TD-DFT? to compute vertical excitation as well as NLO properties using ?global hybrid? (GH) functionals B3LYP and BHandHLYP and ?range separated hybrid? (RSH) functionals CAM B3LY?, wB97, wB97X, and wB97XD with basis set 6?311++G(d,p) and ?correlation consistence polarized valence double and triple zeta? cc-pVDZ and cc-pVTZ respectively in the gas phase and two solvents, N,N-Dimethylformamide (DMF) and ethyl acetate (EA). The trends in absorption and emission values calculated by TD-DFT using all the above mentioned functional and basis sets were studied and it was observed that the trends seen in the computed parameters using B3LYP, BHandHLYP and CAM B3LYP are in good agreement with the trends in experimental values. DFT calculations were performed to determine ?static dipole moment? (mu), ?linear polarizability? (alpha), ?first order hyperpolarizability? (beta0), ?second order hyperpolarizability? (gamma). We have calculated the mean average errors in dipole moment, linear polarizability, first and second hyperpolarizability and vertical excitation. We have observed large values of ?first order hyperpolarizability? (301?938 ¡Á 10^-30 e.s.u) and ?second order hyperpolarizability? (684?2498 ¡Á 10^-34) and they can act as good nonlinear optical materials. Also, vibrational contribution indicates the red shifted absorption and emission in 2c. They show higher values of electrophilicity index which indicates the stability and reactivity of molecules.

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Etude par RMN de composes organiques contenant des chalcogenes – VIII. RMN du 13C dans la chromannone, la chromone, la coumarannone-3 et la coumarine et leurs analogues soufres, selenies et tellures

13C NMR spectra of the title compounds have been fully assigned.The results have been compared with those relative to other chalcogenated compounds, such as anisole, phenyl benzoate, benzofuran,… and their analogs.In chalcogenochromones and -coumarines, the heteroatom lone pair delocalization spreads to some extent over the heterocyclic part of the molecules, while in chalcogenochromanones and -indoxyles, it only extends to the homocycle.This electronic effect seems also to affect the heavy atom effect exhibited by Te-containing compounds.

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