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A gold-catalysed fully intermolecular oxidation and sulfur-ylide formation sequence on ynamides

An efficient C-O, C-S and C-C bond-forming sequence leads to functionalised compounds bearing sulfur-substituted quaternary carbons. Ynamides are employed as diazo-equivalents to access the [2,3]-sigmatropic rearrangements of allyl sulfonium ylides by a three-component chemoselective oxidation and intermolecular ylide formation. the Partner Organisations 2014.

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CH2Cl2 as reagent in the synthesis of methylene-bridged 3,3?-bis(oxazolidin-2-one) derivatives under ambient conditions

This paper describes a highly efficient and facile transformation of substituted oxazolidin-2-ones to methylene-bridged 3,3?-bis(oxazolidin-2- one) derivatives in a mixture solvent of CH2Cl2 (DCM) and N,N-dimethylformamide (DMF) in the presence of NaH at ambient temperature. Isotopic labeling experiments indicated that the C of the bridged methylene group was derived from CH2Cl2 instead of DMF and other unknown substances in the NaH reagent (60% dispersion in mineral oil). the Partner Organisations 2014.

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INHIBITORS OF THE MENIN-MLL INTERACTION

The present invention is directed to inhibitors of the interaction of menin with MLL and MLL fusion proteins, pharmaceutical compositions containing the same, and their use in the treatment of cancer and other diseases mediated by the menin-MLL interaction.

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MONOCYCLIC AND BICYCLIC COMPOUNDS AND METHODS OF USE

Compounds are provided that act as potent antagonists of the CCR1 receptor, and have in vivo anti-inflammatory activity. The compounds are generally monocyclic and bicyclic compounds and are useful in pharmaceutical compositions, methods for the treatment of CCR1-mediated diseases, and as controls in assays for the identification of competitive CCR1 antagonists.

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Oxazolidine – Wikipedia,
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LEMEDES-CO2: A lab for studying degradation of solvents used for CO2 capture post-combustion amine based systems

One key criterion of CO2 capture solvents is their resistance to ageing – A set of thermal and chemical mechanisms – leading to a degradation of the process optimal operation and possible emissions. From literature, many lab-scale studies on solvent degradation are not sufficiently representative of industrial capture conditions. In order to address this issue, EDF R&D decided to set up a lab for studying degradation of solvents used for CO2 capture, named “LEMEDES-CO2”. In particular, LEMEDESCO2 lab-scale apparatus has been designed to reproduce the dynamic cycling of the solvent between the absorber and the stripper columns. The technical features of this original lab-scale apparatus are based on the chemical absorption principle with short cycles of absorption and stripping and a fast heating up and cooling down of the solvent. Using MEA solvent as benchmark case, an important number of degradation products has been detected and most of the species are identified, in agreement with literature. Those results showed this bench scale set up capacity to mimic observed degradation behavior witnessed on industrial pilot plant, thus validating the capacity of the lab-scale experiment to simulate the operating conditions seen by the solvent during cycles of absorption and stripping.

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Oxazolidine – Wikipedia,
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Reaction of Methyl Dithiocarbamates with Amines and Hydrazine. Macrocyclization via Dimethyl 2-Oxo-1,3-imidazolidinebis(carbodithioate)

2-Oxo-1,3-imidazolidinebis(carbothioamide)s and 2,4-dioxo-1-imidazolidinecarbothioamides were prepared by the reaction of dimethyl 2-oxo-1,3-imidazolidinebis(carbodithioate) (1b) and methyl 2,4-dioxo-1-imidazolidinecarbodithioate (2b) with amines, respectively.The reaction of 2-oxazolidone with carbon disulfide gave 2-oxo-3-oxazolidinecarbodithioic acid, the methyl ester of which (4b) led to 2-oxo-3-oxazolidinecarbothioamides.Esters 1b, 2b, and 4b reacted with hydrazine hydrate to give the corresponding thiohydrazides, from which thiosemicarbazone derivatives were obtained.Macrocyclic thioureas were synthesized by the reaction of 1b with aliphatic diamines, polyether-containing diamines, and polyamines.

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A Modular Synthesis of 4-Aminoquinolines and [1,3] N-to-C Rearrangement to Quinolin-4-ylmethanesulfonamides

A copper-catalyzed regiocontrolled three-component reaction afforded diversified 4-aminoquinolines using nitriles, diaryliodoniums, and ynamides. The C7-substituted regioisomers were formed regioselectively when meta-substituted phenyliodonium salts were used. [1,3] N-to-C rearrangement of the products to quinolin-4-ylmethanesulfonamides and simultaneous deprotection of benzyl and sulfonamide group were newly developed. Finally, antimalarial CK-2-68 was successfully prepared.

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Configurational stability of chiral, nonconjugated nitrogen-substituted organolithium compounds generated by tin-lithium exchange of N-[(1-Tri-n-butylstannyl)alkyl]imidazolidin-2-ones and -oxazolidin-2-ones

Chiral, nonracemic, nonconjugated, acyclic nitrogen-substituted organolithium compounds were generated in order to study the configurational stability of such species. The organolithium compounds were generated by tin-lithium exchange on N-[(1-tri-n-butylstannyl)alkyl]imidazolidin-2-ones and N-[(1-tri-n-butylstannyl)alkyl]-oxazolidin-2-ones. Varying degrees of epimerization were observed, depending on the structure of the heterocycle and the reaction conditions. When the nitrogen was part of an imidazolidinone ring, the epimerization was sufficiently slow to be observed at low temperature, thus allowing the configurational stability of nonconjugated, acyclic nitrogen-substituted organolithium compounds to be evaluated for the first time. Addition of the coordinating solvent TMEDA caused a much more rapid epimerization. When the nitrogen was part of an oxazolidinone ring, the rate of epimerization was too fast to observe, even at low temperature. Reaction of these species with electrophiles such as DCl, Bu3SnCl, aldehydes, and ketones proceeded with retention of configuration. A novel method for the synthesis of the chiral stannanes was developed. Condensation of carbamates (cyclic and acyclic) or imidazolidin-2-ones with sodium p-toluenesulfinate, an aldehyde, and formic acid produced N-sulfonylalkylated materials (the Engberts method), which were treated with tri-n-butylstannyl anions to give N-[(1-tri-n-butylstannyl)alkyl]carbamates, -oxazolidin-2-ones, and -imidazolidin-2-ones. When chiral imidazolidin-2-ones were used in the sulfonylalkylation reaction, a single diastereomeric sulfone was produced. Displacement of the sulfone with (tri-n-butylstannyl)lithium proceeded with complete retention of stereochemistry. Evidence for the formation and stereoselective reaction of a nitrogen-substituted radical intermediate was obtained.

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Characterization of interfacial behaviour in carbon-fibre/cyanate composites

In this study an attempt is made to investigate the influence of surface treatments such as oxidation and sizing on a high-strength carbon fibre in respect of interfacial adhesion in composite materials with a cyanate matrix. For analysing the fibre/resin interfacial adhesion the single-fibre pull-out technique has been used. The interfacial shear strengths obtained by this technique have been compared with results of interlaminar shear strength measurements corresponding to woven composite plates. In order to clarify the nature of this interfacial adhesion, both morphological (by atomic force microscopy, AFM) and chemical characterisation (by Fourier transform infrared, FTIR), have also been carried out.

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CHIMIE DES RADIOPROTECTEURS: REVISION DE LA SYNTHESE DES ACIDES S-<(AMINOPROPYL-3)AMINOETHYL-2> ET S-<(N-METHYLAMINOPROPYL-3)AMINOETHYL-2>PHOSPHOROTHIOIQUES

Simple, reproducible and detailed preparations of S-<2-(3-aminopropyl)aminoethyl> and S-<2-(3-N-methylaminopropyl)aminoethyl> phosphorothioic acids (HO)2P(O)-S-(CH2)2-NH-(CH2)3-NH-R (R=H and CH3), named WR 2721 and WR 1680 respectively, are described.The yields of each step have been optimized to facilitate the synthesis of these compounds of large interest in the cancer radio- and chemotherapy.

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