7151-64-6Relevant academic research and scientific papers
CONTROLLED DRUG RELEASE FROM SOLID SUPPORTS
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Page/Page column 31-32, (2011/11/30)
The invention relates to solid supports useful in medical applications that provide controlled release of drugs, such as peptides, nucleic acids and small molecules. The drugs are covalently coupled to the solid support through a linkage that releases the drug or a prodrug through controlled beta elimination.
CONTROLLED RELEASE FROM MACROMOLECULAR CONJUGATES
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Page/Page column 24-25, (2011/11/30)
The invention relates to conjugates of macromolecular carriers and drugs comprising linkers that release the drug or a prodrug through rate-controlled beta-elimination, and methods of making and using the conjugates.
Reactions of diazo compounds with alkenes catalysed by [RuCl(cod)(Cp)]: Effect of the substituents in the formation of cyclopropanation or metathesis products
Basato, Marino,Tubaro, Cristina,Biffis, Andrea,Bonato, Marco,Buscemi, Gabriella,Lighezzolo, Filippo,Lunardi, Pamela,Yianini, Chiara,Benetollo, Franco,Del Zotto, Alessandro
experimental part, p. 1516 - 1526 (2009/09/04)
The reaction of diazo compounds with alkenes catalysed by complex [RuCl(COd)(Cp)] (cod = 1, 5-cyclooctadiene, Cp = cyclopentadienyl) has been studied. The catalytic cycle involves in the first step the decomposition of the diazo derivative to afford the reactive [RuCl(Cp)I=C(R1)R 2)] intermediate and a mechanism is proposed for this step based on a kinetic study of the simple coupling reaction of ethyl diazoacetate. The evolution of the Ru-carbene intermediate in the presence of alkenes depends on the nature of the substituents at both the diazo N2=C(R 1)R2 (R1, R2 = Ph, H; Ph, CO 2Me; Ph, Ph; C(R1)R2 = fluorene) and the olefin substrates R3(H)C= C(H)R4 (R3, R4 = CO2Et, CO2Et; Ph, Ph; Ph, Me; Ph, H; Me, Br; Me, CN; Ph, CN; H, CN; CN, CN). A remarkable reactivity of the complex was recorded, especially towards unstable aryldiazo compounds and electron-poor olefins. The results obtained indicate that either cyclopropanation or metathesis products can be formed: the first products are favoured by the presence of a cyano substituent at the double bond and the second ones by a phenyl.
Studies of the Borderline between Concerted and Stepwise Mechanisms of Elimination : E1cB Elimination of Fluoren-9-ylmethyl Carboxylate Esters
O'Ferrall, Rory A. More,Larkin, Finbar,Walsh, Peter
, p. 1573 - 1580 (2007/10/02)
Rates of β-elimination of carboxylate leaving groups from fluoren-9-ylmethyl carboxylate esters in methanolic sodium methoxide at 25 deg C are reported.An E1cB mechanism with rate-determining formation of a carbanion intermediate is assigned on the basis of near identity of measured elimination rates and rates of carbanion formation predicted from a Taft correlation, and the similarity with elimination of 1-(1-acetoxy-1-methylethyl)indene for which the mechanism has been established by Ahlberg and Thibblin.Values of ρ=0.42 and βlg=0.27 measured for substituted benzoate leaving groups are a little larger than expected (ca. 0.24 and 0.18, respectively) and the discrepancy is tentatively ascribed to conformational enhancement of remote substituent effects, rather than to a contribution of E2 elimination.The effects of alkyl and aryl substitution α to the leaving group are discussed, especially in relation to the borderline between concerted and stepwise mechanisms.The measurements fail to confirm an earlier inference that the borderline shows a discontinuity in transition-state structure at the point of mechanistic change.
Diels-Alder Reaction: 1,4-Cycloaddition of N-Aryl-maleimides to Alkylidene- and Arylidene-fluorenones and Synthesis of Some New Fluoranthene Derivatives
Abdou, Sadek E.,Habashy, Adiba,Aziz, Gamil,Khalifa, Fathy
, p. 755 - 758 (2007/10/02)
The 1,4-cycloaddition of different N-arylmaleimides (IIa-f) to alkylidene- and arylidene-fluorenones (Ia-c) leads to the formation of the diadducts, 7-substituted-5-aryl-4,6-dioxo-4H-3,3a,5,6,6a,7,10b-octahydrofluoranthenopyrrole-endo(3,10b)-N-arylpyrrolidino-2',5'-diones (IIIa-r).The fully aromatized fluoranthene derivatives (Va-i) have also been synthesised either by boiling III in nitrobenzene or by reacting the bromo-derivatives (V) with appropriate II.Reduction of III using LAH gives VIII.The structures of the isolated products have been confirmed by elemental analyses, molecular weight determination and spectroscopic data.
Photo-induced Reduction of Fluoren-9-ol and its Acetate by Aliphatic Amines
Ohashi, Mamoru,Furukawa, Yuji,Tsujimoto, Kazuo
, p. 2613 - 2616 (2007/10/02)
Irradiation of fluoren-9-ol and its acetate in the presence of an aliphatic amine gave fluorene as the major product.The yield of fluorene depended upon the character of amine and increased in the order of primary methanol and acetonitrile) it was revealed that the major process was electron transfer followed by proton transfer.A radical reaction also participated as a minor process.A possible reaction mechanism similar to the photo-induced Birch reduction was proposed.
