30649-18-4Relevant academic research and scientific papers
Enolization of aldehydes and ketones: Structural effects on concerted acid-base catalysis
Hegarty, Anthony F.,Dowling, Joseph P.,Eustace, Stephen J.,McGarraghy, Michelle
, p. 2290 - 2296 (1998)
The third-order term (k(AB)) for the concerted acid-base catalyzed enolization of a selection of simple aldehydes and ketones has been measured in a series of substituted acetic acids at 25°C at constant ionic strength 2.0 (NaNO3). While there is no direct correlation of the magnitude of the third-order term with either the rate constants for acid (k(A)) or base (k(B)) catalysis, a simple log-log relationship exists between the product of the consecutive rate constants (k(A)·k(B)) and the concerted (third order) rate constants (k(AB)). This implies that the concerted pathway is important only when both the general acid and the general base terms are significant; this will be useful in designing other systems which might show such concerted catalysis. In the case of aldehydes, a slope of 0.97 was found for this plot, which compares to the result for 4-substituted cyclohexanones (0.51) and other ketones (0.59), as measured in acetic acid buffers. The resultant Bronsted β(AB) value of 0.20 found for propanal (2) is consistent with the overall observation that concerted catalysis is largely independent of the buffering species, and that process is overall base catalyzed. The solvent isotope effect on the concerted acid-base catalyzed enolization rate term, k(AB)(H2O)/k(AB)(D2O) = 1.33, indicates that the transition state for proton transfer to the carbonyl is more advanced than in the case of ketones. In general we have found that carbonyl compounds with large measured (or estimated) enol contents show significant third-order terms.
Pd(II)-catalyzed sequential C-C/C-O bond formations: A new strategy to construct trisubstituted furans
Zheng, Meifang,Huang, Liangbin,Wu, Wanqing,Jiang, Huanfeng
, p. 1838 - 1841 (2013/06/04)
Palladium-catalyzed oxidative difunctionalization of enol ethers with 1,3-dicarbonyl compounds to construct trisubstituted furans in one step under mild conditions is described. The reaction is thought to proceed through a C-C bond formation along with a C-O bond closing the ring structure. Oxygen is the sole oxidant regenerating the Pd(II) catalyst.
Isolation and synthesis of analgesic and anti-inflammatory compounds from Ochna squarrosa L.
Anuradha,Srinivas, Pullela V.,Ranga Rao,Manjulatha,Purohit, Muralidhar G.,Madhusudana Rao
, p. 6820 - 6826 (2007/10/03)
Two new furanoflavonoids (1, 2), one new chalcone dimer (3) along with six known compounds, chrysophanol, 5-O-methyl squarrosin, 5-methoxy furano[4″,5″,6,7]flavone, calodenone, lophirone A and lophirone H were isolated from the ethyl acetate-soluble fraction of methanol extract of root bark of Ochna squarrosa. Chrysophanol, calodenone, lophirone A and lophirone H were isolated from this plant for the first time. The structures of all the isolated compounds were confirmed by 1D and 2D spectroscopic data. These compounds were tested for analgesic and anti-inflammatory activity. All the new compounds showed good analgesic and anti-inflammatory activity. A simple and facile method for the cleavage of benzyl ethers using I2 in trigol is also reported.
Tetrabutylammonium tribromide (TBATB)-promoted tetrahydropyranylation/depyranylation of alcohols
Naik, Sarala,Gopinath, Rangam,Patel, Bhisma K
, p. 7679 - 7681 (2007/10/03)
Alcohols are tetrahydropyranylated rapidly in high yields in the presence of a catalytic amount of TBATB in dichloromethane at room temperature. Depyranylation to their parent alcohol is achieved in quantitative yields by merely changing the solvent to methanol.
Oxidative deprotection of silylethers, acetals and ketals by oxygen or air in presence of manganese and cobalt salts of 4-aminobenzoic acid supported on silica gel as catalyst
Hashemi, Mohammed M.,Kalantari, Fariba
, p. 1857 - 1863 (2007/10/03)
Oxidative deprotection of silylethers, acetals and ketals, to their corresponding alcohols, aldehydes and ketones have been achieved using oxygen or air in the presence of cobalt and manganese salts of 4-aminobenzoic acid supported an silica gel as catalysts. Reactions are clean and catalysts can be recovered easily and reused repeatedly.
An Investigation on Desilylation of Alkyl and Phenolic Silyl Ethers Using FeCl3
Saravanan, Parthasarathy,Singh, Vinod K.
, p. 565 - 567 (2007/10/03)
A variety of alkyl and phenolic TBDMS ethers have been efficiently cleaved using anhydrous FeCl3 in MeOH under mild conditions. It was found that choice of solvent is crucial for the rate of the deprotection of TBDMS ether with FeCl3.
Phenylacetaldehyde and its cis- and trans-Enols and Enolate Ions. Determination of the cis:trans Ratio under Equilibrium and Kinetic Control
Chiang, Y.,Kresge, A. J.,Walsh, P. A.,Yin, Y.
, p. 869 - 871 (2007/10/02)
A method of determining individual keto-enol equilibrium and acid dissociation constants for systems in which unstable enols can exist in cis and trans isomeric forms is developed and is applied to phenylacetaldehyde in aqueous solution; the results give equilibrium cis:trans ratios of 35 : 65 in acidic and neutral solutions and 20 : 80 in a basic colution (where the enols are converted to enolate ions), but show considerably less cis:trans differentiation for enols formed under kinetic control.
Stereospecific synthesis of isocephalosporins and 2-oxa isocephalosporins
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, (2008/06/13)
A process is described whereby a synthetically produced 4-styryl-cis-3,4-azetidinone is converted to an isocephalosporin or its 2-oxa analog. The process is based upon the condensation of enamine and imine synthons. Novel intermediate azetidinones are also disclosed. Control of the stereochemical course of the process allows economical, high yield preparation of the racemic form of the product or when a single enantiomer of the imine synthon derived from the β-hydroxy-α-amino acid starting material is used, both enantiomers of the product may be prepared and separated without optical resolution.
Kinetic Acidity Function Hc. Part 3. Applicability to Hydration of Styrenes
Ellis, Graham W. L.,Johnson, C. David
, p. 1025 - 1028 (2007/10/02)
Variation of rate of hydration of substituted styrenes with acidity has been measured in aqueous sulphuric acid solutions.This reaction proceeds through a rate-limiting carbon protonation step.Linear Pfluger plots of unit slope result from the data.These appear to validate the applicability of an acidity function to the results; possible sources of error in this and related conclusions are carefully discussed.
Transformation of Acyclic Ketones into Aldehydes and Ketones with Substituted Side Chains
Tietze, Lutz-F.,Kinast, Guenther
, p. 451 - 460 (2007/10/02)
Aminomethylation of the acyclic ketones 1/2 leads to the aminoketones 3/4 which give, after reduction, quaternisation and ion exchange or previous reaction with a Grignard reagent, the hydroxyammonium compounds 9/10 and 14, respectively.Flash thermolysis of 9/10 yields the aldehydes 7 and of 14 the ketone 15 in which one side-chain of the educt 2b is substituted by the alkyl group of the Grignard reagent.
