Search results for "Reactive intermediate"
showing 10 items of 18 documents
Role of the functional group in n-octydimethylsilanes in the synthesis of C8 reversed-phase silica packings for high-performance liquid chromatography
1986
Abstract C8 reversed-phase packings have been sysnthesised by reaction of a 25-nm pore-size high-performance liquid chromatographic silica (10 μm, as(BET) = 297 m2 g-1) with 2,4-lutidine as base and dichloromethane and N,N-dimethylflormamide as solvents, or without solvents and with the following silanes: n-octyldimenthylchlorosilane (C8-Cl), n-octyldimethylhydroxysilane (C8-OH), n-octyldimethylmethoxysilane (C8-OCH3), n-octyldimethylethoxysilane (C8-OC2H5), n-octyldimethyl(dimethylamino) silane [C8-N(CH3)2], n-octyldimethyl(trifluoroacetoxy)silane (C8- OCOCF3), and bis-(n-octyldimethylsiloxane) (C8-O-C8). C8-Cl, C8-OH and C8-OCH3 each form a reactive intermediate with 2,4-lutidine, favouri…
The Chemistry of Unsaturated Nitrogen–Heterocyclic Compounds Containing Carbonyl Groups
1993
Publisher Summary Most hydroxy-substituted azaheteroaromatic compounds exist predominately in the NH/carbonyl tautomeric form, and these compounds have been widely discussed. This chapter provides an overview of azaheteroaromatic compounds and I-azetin-4-ones—these are those azaheterocycles that contain in the ring at least one carbonyl group and one or two nitrogen atoms in the form of C=N or N=N bonds. Many of these compounds are unstable but their importance as reactive intermediates is established, and many of them could be used as synthons in the preparation of pharmacologically active compounds. The chapter describes the free existence of I-azetin-4-one and the nucleophilic substituti…
Racemic and Optically Pure Heptahelicene-2-carboxylic Acid: Its Synthesis and Self-Assembly into Nanowire-Like Aggregates
2010
Heptahelicene-2-carboxylic acid was effectively synthesised from suitably functionalised naphthalene building blocks. Methoxy-substituted 1,1'-ethyne-1,2-diylbis(2-but-3-yn-1-ylnaphthalene) was cyclised in the presence of CpCo(CO)(2)/PPh(3) to 2-methoxy-7,8,11,12-tetrahydroheptahelicene, which was converted into heptahelicen-2-yl trifluoromethanesulfonate. This reactive intermediate underwent Pd(OAc)(2)/dppp-catalysed methoxycarbonylation reaction to provide, after hydrolysis, heptahelicene-2-carboxylic acid. The racemate was resolved into enantiomers by semipreparative HPLC on a chiral column. The helicity of (+)-(P)-heptahelicene-2-carboxylic acid was assigned by correlating its CD spectr…
ChemInform Abstract: Radical Addition to Iminium Ions and Cationic Heterocycles
2015
Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta react…
XAFS Studies of High-Valent Porphyrinato Manganèse Complexes with Ozone
1997
We produce strong evidence of the interaction of ozone with a series of Manganese (III) porphyrinato complexes to form a well defined reactive intermediate. In the latter species, the Manganese atom which is formally in a tetravalent (IV) state, is (at least) hexacoordinated with the metal unambiguously lying in the basal plane of the four pyrrolic nitrogens of the porphyrin macrocycle. Substitution of Bromine or Chlorine axial ligands by ozonids is most likely to happen. This conclusion is also supported by XANES and EXAFS spectra recorded at the Chlorine K-edge which suggest that ozone may even form with chlorine a complex anion.
Cyclic Sulfonimidates by Dynamic Diastereomer-Differentiating Cyclisation: Large-Scale Synthesis and Mechanistic Studies
2001
A dynamic diastereomer differentiating cyclisation is the key step in a new large-scale synthesis of both enantiomers of the cyclic sulfonimidates 1 (Aldrich no. 54099-4) and ent-1 (Aldrich no. 54412-4). These are valuable starting materials in the asymmetric synthesis of chiral oxa- and azaheterocyclic compounds. NMR spectroscopic studies on the reacting system reveal N-chloro sulfinamides to be reactive intermediates in the oxidative chlorination of sulfinamides with tert-butyl hypochlorite and allow for the inspection of the configurational behaviour of the involved sulfonimidoyl chlorides and sulfonimidoyl bromides.
Sulfur Dioxide Oxidation Catalyzed by Photosensitized Ytterbium Diphthalocyanine
2008
Oxidation of SO2 into SO3 was found effectively catalyzed by photosensitized ytterbium diphthalocyanine, YbPc2 (Pc = phthalocyanine ligand, C32H16N8) when performed in air-saturated dimethylformamide (DMF) solution at 20 °C. The process follows according to a multi-step complex mechanism involving chemical induction as its driving force. Excitation energy of the sandwich molecular system in YbPc2 is used to promote the reaction by creating a reactive intermediate form of the ytterbium complex hosting up to eight SO2 molecules. The conversion of SO2 proved complete.
Orthometalation reactions in trifluoroacetate dirhodium(II) compounds. Molecular structure of Rh2(O2CCF3)2[(C6H4)PPh2]2·(PPh3)2·2(C7H8)
1994
Abstract Rh 2 (O 2 CCF 3 ) 3 [(C 6 H 4 )PPh 2 ]·(HO 2 CCF 3 ) 2 reacts with PPh 3 yielding the doubly metalated compound Rh 2 (O 2 CCH 3 ) 2− [(C 6 H 4 )PPh 2 ] 2 ·(HO 2 CCF 3 ) 2 . The reaction proceeds via a reactive intermediate with an equatorial phosphine, Rh 2 (η 2 -O 2 CCF 3 )(μ-O 2 CCF 3 ) 2 [(C 6 H 4 )PPh 2 ](PPh 3 )·(HO 2 CCF 3 ), which can also be generated in moderate yield under photochemical conditions. The structure of the PPh 3 bis-adduct Rh 2 (O 2 CCF 3 ) 2 [(C 6 H 4 )PPh 2 ] 2 ·(PPh 3 ) 2 ·2(C 7 H 8 ) has been determined by X-ray diffraction. M r =1663.27, orthorhombic, space group Fdd 2, a =41.748(9), b =21.620(5), c =17.375(5) A, V =15683(6) A 3 , Z =8, D x =1.41 g cm −3…
Exhalation of ethylene oxide by rats on exposure to ethylene.
1983
Abstract When rats are exposed to ethylene in a closed desiccator jar chamber, the rate of metabolic elimination of the compound is influenced by pretreatment with Aroclor 1254 (metabolism increased) and diethyldithiocarbamate (metabolism inhibited). Biotransformation of ethylene leads to ethylene oxide as reactive intermediate. This is exhaled and can be quantitated in the gas phase of the system.
Photo-inhibition of Ab fibrillation mediated by a newly designed fluorinated oxadiazole
2015
Uncontrolled aggregation of amyloid beta peptide (A?) is the main cause of Alzheimer's Disease. Therapeutic approaches of intervention in amyloid diseases include the use of small molecules able to stabilize the soluble A? conformation, or to redirect the amyloidogenic pathway towards non-toxic and non-fibrillar states. Fluorometric measurements revealed that the 3-(4'-trifluoromethylphenyl)-5-(4'-methoxyphenyl)-1,2,4-oxadiazole, when irradiated, is able to interact with monomeric A? peptide readdressing the aggregation pathway toward the formation of amorphous aggregates as evidenced by means of CD, AFM, and SAXS measurements. We hypothesize that this compound, under radiation, forms a rea…