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A-Dicarbonyls

Analysis Our methods for making 1,2-dioxygenated compounds (frames 154-157) involve reductive linking of a dicarbonyl compound ... [Pg.95]

The C—C double bond in the cyclopentene ring can be cleaved by the osmium tetroxide-periodate procedure or by photooxygenation. The methoxalyl group on C-17 can, as a typical a-dicarbonyl system, be split off with strong base and is replaced by a proton. Since this elimination occurs with retention of the most stable configuration of the cyclization equi-hbrium, the substituents at C-17 and C-18 are located trans to one another. The critical introduction of both hydrogens was thus achieved regio- and stereoselectively. [Pg.259]

Synthesis and Properties. A number of monomers have been used to prepare PQs and PPQs, including aromatic bis((9-diamines) and tetramines, aromatic bis(a-dicarbonyl) monomers (bisglyoxals), bis(phenyl-a-diketones) and a-ketones, bis(phenyl-a-diketones) containing amide, imide, and ester groups between the a-diketones. Significant problems encountered are that the tetraamines are carcinogenic, difficult to purify, and have poor stabihty, and the bisglyoxals require an arduous synthesis. [Pg.536]

K N O R R Pyrazole Synthesis Pyrazole synthesis from a -dicarbonyl compourxi arxi a hydrazine. [Pg.206]

Synthesis of fused cyciopentanones (bicyciotS 3 0] octachones) or of propeltanes from a-dicarbonyl compounds wa the double aktol condensation with etoesters 2... [Pg.408]

One-electron reduction of a-dicarbonyl compounds gives radical anions known as setnidiones. Closely related are the products of one-electron reduction of aromatic quinones, the semiquinones. Both semidiones and semiquinones can be protonated to give neutral radicals which are relatively stable. [Pg.682]

Fluorine Containing a-Dicarbonyl Compounds and Their Densatives (Russ ) Saloutm V L, Pashkevich, K 1, Postovskii,[ Y Usp Khun 51 1287 1304 97... [Pg.16]

This type of synthesis has been used extensively in the preparation of hydroxamic acids resembling aspergillic acid. a-Aminohj droxamic acids react with a-dicarbonyl compounds to yield pyrazine hydroxamic acids (18). Glyoxal and diacetyl react readily, but poor... [Pg.206]

The major developments of catalytic enantioselective cycloaddition reactions of carbonyl compounds with conjugated dienes have been presented. A variety of chiral catalysts is available for the different types of carbonyl compound. For unactivated aldehydes chiral catalysts such as BINOL-aluminum(III), BINOL-tita-nium(IV), acyloxylborane(III), and tridentate Schiff base chromium(III) complexes can catalyze highly diastereo- and enantioselective cycloaddition reactions. The mechanism of these reactions can be a stepwise pathway via a Mukaiyama aldol intermediate or a concerted mechanism. For a-dicarbonyl compounds, which can coordinate to the chiral catalyst in a bidentate fashion, the chiral BOX-copper(II)... [Pg.182]

Alkenes with at least one vinjdic hydrogen undergo oxidative cleavage when treated with ozone, yielding aldehydes (Section 7.9). If the ozonolysis reaction is carried out on a cyclic alkene, a dicarbonyl compound results. [Pg.698]

More than 50 endogenous and exogenous inhibitors of the calpains have been described as either transition-state reversible or irreversible inhibitors. The first transition-state inhibitors were the peptide aldehydes (e.g., leupeptin). Using this compound, new ones were synthesized that exhibited improved membrane permeability and calpain specificity (e.g., calpeptin). Other groups of inhibitors have since been discovered a-dicarbonyls (originally developed as serine protease inhibitors), nonpeptide quinolinecarboxamides,... [Pg.313]

The first step in the nonreversible degradation reactions is the formation of a reactive a-dicarbonyl species through the p-elimination of a hydroxide ion. The subsequent reaction pathways to all degradation products can be described by just five reaction types, namely, p-elimination, benzilic acid rearrangement, a-dicarbonyl cleavage, aldol condensation, and retro-aldol condensation (see Fig. 7).31 Retro-aldol condensation and a-dicarbonyl cleavage involve C-C bond... [Pg.451]

De Bruijn et al.26 30 used chromatographic and spectroscopic techniques to analyze the effect of reaction variables (such as pH and monosaccharide concentration) on the product profile and developed a reaction model (see Fig. 9) that emphasized the role of a-dicarbonyl compounds. Some of the features of the model shown in Fig. 9 are ... [Pg.453]

Tuazon EC, H MacLeod, R Atkinson, WPL Carter (1986) a dicarbonyl yields from the NOj.-air photooxidations of a series of aromatic hydrocarbons in air. Environ Sci Technol 20 383-387. [Pg.47]

The band at 1994 cm observed at low CO coverage, was assigned to a monocarbonyl Rh(CO) species. The nature of the species observed at 2117cm has been elucidated using mixtures of different CO isotopes. As shown in Fig. 4, the band splits into three bands after adsorption of CO/ CO mixtures proving the presence of a dicarbonyl species... [Pg.121]

Rh(CO)2 [16]. Such a dicarbonyl should possess two vibration modes. However, only the symmetric mode is observable in the IR spectrum. The asymmetric mode is inaccessible to an IR experiment on a metal surface due to the so-called metal surface selection rule, which prohibits the observation of dipole excitation if the transition dipole moment is oriented parallel to the surface. It should be noted that the observed frequencies fit well to values observed for Rh(CO)2 on technical Rh/Al203 catalysts [35-40] ( 2100 cm ) and Rh(CO)2 on planar TiO2(110) surfaces [41] (2112 cm ). [Pg.122]

Selenium dioxide can be used to oxidize ketones and aldehydes to a-dicarbonyl compounds. The reaction often gives high yields of products when there is a single type of CH2 group adjacent to the carbonyl group. In unsymmetrical ketones, oxidation usually occurs at the CH2 that is most readily enolized.255... [Pg.1143]

A mixture of 1,4-dioxane and water is often used as the solvent for the conversion of aldehydes and ketones by H2Se03 to a-dicarbonyl compounds in one step (Eq. 8.117).331 Dehydrogenation of carbonyl compounds with selenium dioxide generates the a, (i-unsaturated carbonyl compounds in aqueous acetic acid.332 Using water as the reaction medium, ketones can be transformed into a-iodo ketones upon treatment with sodium iodide, hydrogen peroxide, and an acid.333 Interestingly, a-iodo ketones can be also obtained from secondary alcohol through a metal-free tandem oxidation-iodination approach. [Pg.281]

The pyranocoumarin 105 can be prepared via a three-component Diels-Alder reaction between 4-hydroxycoumarin, ethyl vinyl ether and an a-dicarbonyl compound. Similarly to the above, upon treatment of 105 with sulfuric acid in THF, hydrolysis and rearrangement occur to give the furofurochromenone 106. The hemiacetal functionality in 106 may then be oxidized with pyridinium chlorochromate (PCC) to give the lactone 107 <2001EJ03711> (Scheme 28). [Pg.791]

A methodology described previously (Equation 11) has been successfully used to synthesize compounds 67 by intermolecular cyclization of acyclic tetraamine 137 with a-dicarbonyl reagents. This one-pot preparation furnishes... [Pg.1024]

The reaction of 2-amino-2-deoxy-D-glucose (D-glucosamine) with a dicarbonyl compound was carried out for the first time by Pauly and Ludwig,91 who were trying to discover how pyrrole rings in natural products are formed. They heated free D-glucosamine and ethyl acetoacetate on a steam bath and obtained a substance in which the presence of the pyrrole ring was demonstrated by the pine-splinter test. [Pg.107]

In the presence of bis(acetylacetonato)nickel, a-dicarbonyl compounds readily add at the nitrile group of 4-R-substituted l,2,5-oxadiazole-3-carbonitriles 219 to form enaminofurazans 220. The adducts obtained from 4-amino-3-cyanofurazan underwent intramolecular cyclization upon heating with acetic acid in ethanol to give furazano[3,4- ]pyridine 221 derivatives in high yields (Scheme 51) <2001RCB1280>. [Pg.357]

Strecker aldehyde are generated by rearrangement, decarboxylation and hydrolysis. Thus the Strecker degradation is the oxidative de-amination and de-carboxylation of an a-amino acid in the presence of a dicarbonyl compound. An aldehyde with one fewer carbon atoms than the original amino acid is produced. The other class of product is an a-aminoketone. These are important as they are intermediates in the formation of heterocyclic compounds such as pyrazines, oxazoles and thiazoles, which are important in flavours. [Pg.17]

One possible assignment of the 2110 cm"1 feature is to vibrations involving a dicarbonyl, RhI(C0)2, surface species (30) however, this seems unlikely since the anticipated band partner (30) is absent. Most likely, the 2110 cm"1 band signals the appearance of CO bound to "oxidized rhodium sites, where rhodium has undergone formal oxidation to Rh(I) or Rh(III), and/or adjacent to sites where surface oxide has formed (3d ). A similar high-frequency vco feature has been observed at supported rhodium exposed to gaseous C02 and 02 (21). [Pg.316]


See other pages where A-Dicarbonyls is mentioned: [Pg.151]    [Pg.44]    [Pg.180]    [Pg.428]    [Pg.206]    [Pg.125]    [Pg.175]    [Pg.130]    [Pg.451]    [Pg.452]    [Pg.454]    [Pg.455]    [Pg.455]    [Pg.16]    [Pg.124]    [Pg.1157]    [Pg.287]    [Pg.72]    [Pg.99]    [Pg.406]    [Pg.408]    [Pg.78]    [Pg.14]    [Pg.35]    [Pg.151]   
See also in sourсe #XX -- [ Pg.506 ]

See also in sourсe #XX -- [ Pg.8 , Pg.262 ]




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1.3- Dicarbonyl compounds a-alk-l-ynylation

A-Dicarbonyl compounds

A-Dicarbonyls synthesis

A-dicarbonyl

Dicarbonyl Compounds as Nucleophiles

Dicarbonyl Compounds with a-Amino Acids

Dicarbonyl compounds, a-selenooxidative syn elimination

Dicarbonyl compounds, a-selenooxidative syn elimination synthesis

Of a dicarbonyls

Oxidation of Ketones to a-Dicarbonyl Compounds

Reaction of a,3-Dicarbonyl Compounds with Ammonia

Synthesis of TMs with a 1,6-Dicarbonyl Pattern

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