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The synthesis of pyrano[2,3-b]quinoxalines related to molybdopterin

Two cobalt complexes, 5 and 7, both containing 11,11a-dihydropyrano[2,3-b]quinoxaline nuclei, were synthesised as model substances for the molybdenum cofactor of the oxomolybdoenzymes. The organic proligands for the ene-1,2-dithiolates, from which these complexes were formed, were 1,3-dithiol-2-ones, the dianionic ligands being liberated by reaction with caesium hydroxide. The pyran ring in the tetracyclic 1,3-dithiol-2-one proligands, 4b and 6, was formed by ring closure of the side-chain alcohol in 4-(1-hydroxyalkyl)-5-(quinoxalin-2-yl)-1,3-dithiol-2-one onto an aromatic quinoxaline via reaction with a chloroformate, generating 6-alkyloxycarbonyl-2-oxo-5a,6-dihydro-4H-[1,3]dithiolo[4′,5′:4,5]pyrano[2,3-b]quinoxalines which were then reduced with cyanoborohydride to give 6-alkyloxycarbonyl-5a,6,11,11a-tetrahydro-2-oxo-4H-[1,3]dithio[4′,5′:4,5]pyrano[2,3-b]quinoxalines – the proligands.

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Lewis acid-catalyzed generation of C-C and C-N bonds on pi-deficient heterocyclic substrates

Focused microwave irradiation of a series of halogenated nitrogen heterocycles and different kinds of nucleophiles in the presence of a catalytic amount of indium trichloride leads to the efficient and completely regioselective generation of aromatic C-C and C-N bonds. The method is simple, rapid, general and inexpensive, and can be performed without the use of dried solvents. Most of the synthetized compounds are new and in many cases the work-up required only filtration. Furthermore, this is the first example of the use of a Lewis acid as a catalyst for heteroarylation, vinylation and amination reactions on pi-deficient heterocyclic substrates.

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Cosmetic compositions comprising polymers comprising complementary chemical functional groups

Cosmetic compositions comprising at least two polymers comprising complementary chemical functional groups, capable of forming a coat on a keratin material, such as hair, a cosmetic process comprising the use of these polymers on the keratin material, such as the hair, and also their use for producing a coat on the hair.

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Catalyst-free and base-free water-promoted SNAr reaction of heteroaryl halides with thiols

A simple and efficient route for the synthesis of biaryl sulfides have been developed in aqueous medium under base- and catalyst-free conditions. A wide variety of heteroaryl halides and thiols underwent SNAr reaction to provide diaryl sulfides in good to excellent yields. The remarkable key features of the reaction include the use of water as an inexpensive and environmentally benign reaction medium, absence of any additional reagent or catalyst, and easy isolation of the products. Georg Thieme Verlag Stuttgart.

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A new type of ketolide bearing an N-aryl-alkyl acetamide moiety at the C-9 iminoether: Synthesis and structure-activity relationships (2)

A new type of ketolide bearing an N-aryl-alkyl acetamide moiety at the C-9 iminoether and its analogues were prepared, and their antibacterial activities and pharmacokinetic properties were evaluated. We found that the introduction of an (R)-alkyl group between the amide and iminoether groups could improve the pharmacokinetic properties while maintaining the activity against erythromycin-resistant Streptococcus pneumoniae. Among the ketolides prepared with the (R)-alkyl group, compound 5p with an N-(3-quinoxalin-6-yl-propyl)-propionamide moiety was found to have in vivo efficacy comparable to CAM with potent in vitro antibacterial activities against the key respiratory pathogens including Haemophilus influenzae and erythromycin-resistant S. pneumoniae.

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Nickel-Catalyzed C-N Cross-Coupling of Ammonia, (Hetero)anilines, and Indoles with Activated (Hetero)aryl Chlorides Enabled by Ligand Design

The Ni(II) precatalyst (C1) featuring the phosphonite ancillary ligand Phen-DalPhos (L1) was employed in the cross-coupling of (hetero)anilines with (hetero)aryl chlorides and in the diarylation of ammonia with (hetero)aryl chlorides to afford heteroatom-dense di(hetero)arylamines. The PAd2-DalPhos precatalyst C4 provided complementary reactivity in cross-couplings of indoles with (hetero)aryl chlorides. Taken together, the demonstration of room-temperature reactivity within each of the reaction classes examined and the observation of useful chemoselectivity at low loading (?0.5 mol % Ni) and on gram-scale distinguishes C1 and C4 from other metal catalysts (i.e., copper, palladium, nickel, or other) within the field of C-N cross-coupling chemistry.

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Silver(I)-catalyzed synthesis of novel quinoxaline derivatives

The one-pot reaction of 2-chloroquinoxaline with phenoxide ion derivatives utilizing Ag+ as catalyst provided an efficient method for the preparation of five novel quinoxaline derivatives.

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Efficient Phosphorus-Free Chlorination of Hydroxy Aza-Arenes and Their Application in One-Pot Pharmaceutical Synthesis

The chlorination of hydroxy aza-arenes with bis(trichloromethyl) carbonate (BTC) and SOCl2 has been effectively performed by refluxing with 5 wt % 4-dimethylaminopyridine (DMAP) as a catalyst. Various substrates are chlorinated with high yields. The obtained chlorinated aza-arenes can be used directly with simple workup for succedent one-pot synthesis on a large scale.

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Experimental and computational studies on propanone derivatives of quinoxalin-6-yl-4,5-dihydropyrazole as inhibitors of mild steel corrosion in hydrochloric acid

Two quinoxaline-based propanones, 1-[3-(3-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]propan-1-one (Mt-3-PQPP) and 1-(3-(4-chlorophenyl)-5-(quinoxalin-6-yl)-4,5-dihydro-1H-pyrazol-1-yl)propan-1-one (Cl-4-PQPP) were tested as inhibitors of mild steel corrosion in 1 M HCl using both experimental and computational approaches. Both compounds were found to retard corrosion rate of mild steel in the studied medium. Mt-3-PQPP and Cl-4-PQPP exhibited mixed-type inhibitive action, reducing the rate of anodic and cathodic corrosion reactions, as suggested by Tafel polarization measurements. Adsorbed molecules of Mt-3-PQPP and Cl-4-PQPP formed pseudo-capacitive film on mild steel surface in 1 M HCl as proposed by electrochemical impedance spectroscopy (EIS) measurements. Adsorption surface coverage data were fitted into the Langmuir adsorption isotherm and the evaluated thermodynamic parameters suggested chemisorption for Mt-3-PQPP and competitive physisorption and chemisorption for Cl-4-PQPP. Scanning electron microscopy (SEM) analyses further revealed that adsorbed film of the inhibitor molecules protected the steel from direct exposure to acidic ions. Quantum chemical calculations suggested that higher corrosion inhibition efficiency of Mt-3-PQPP compared to Cl-4-PQPP molecule is due to the higher electron donating tendency of the former. Mt-3-PQPP molecule also showed higher protonation tendency in the acid than Cl-4-PQPP and its protonated form showed better corrosion inhibition potentials than that of Cl-4-PQPP. Monte Carlo simulation of the adsorption of Mt-3-PQPP and Cl-4-PQPP molecules on Fe(1 1 0) surface also confirmed higher adsorption energy for the former.

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Development of CXCR3 antagonists. Part 4: Discovery of 2-amino-(4-tropinyl)quinolines

The synthesis and biological evaluation of a novel series of 2-aminoquinoline substituted piperidines and tropanes incorporating a homotropene moiety is herein described. The series exhibits potent antagonism of the CXCR3 receptor and superior physicochemical properties. Compound 24d was found to be orally bioavailable, and PK/PD studies suggested it as a suitable tool for studying the role of CXCR3 in models of disease.

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