Triarylmethanes and 9-arylxanthenes as prototypes amphihydric compounds for relating the stabilities of cations, anions and radicals by C-H bond cleavage and electron transfer
摘要:
Thermodynamic stability properties of II p-substituted trityl and seven 9-phenylxanthyl carbocations are reported in sulfolane and of their conjugate carbanions in DMSO. The cations are compared by calorimetric heats of hydride transfer from cyanoborohydride ion, their first and second reduction potentials, their PK(R)(+)s in aqueous sulfuric acid, C-13 chemical shifts and free energies of methoxy exchange. Carbanlons are compared by their heats and free energies (pK(HA)) of deprotonation and their first and second oxidation potentials. Radicals are compared by their oxidation and reduction potentials. Their bond dissociation energies are derived by alternative routes: from the carbocation and its reduction potential and from the carbanion and its oxidation potential. The various properties are correlated against each other and against appropriate Hammett-type substituent parameters. Correlations between the different measured properties reported here range from fair to excellent, Despite their importance as historic prototypes for the three trivalent oxidation states of carbon, trityl and xanthyl systems are atypical models for comparing transmission of electron demand In other series of carbocations, radicals or carbanions with significantly different structures. The 9-arylxanthyl series is especially poor because of its insensitivity to substituent effects. The effects of substituents on various properties which represent the stabilities of R(+)s correlate surprisingly well against those for corresponding R(-)s. Accordingly, compensating effects on the oxidation and reduction of a series of related RS may lead to a nearly constant electron transfer energy and absolute hardness for the series. In contrast, the free energies for interconversion of the carbocations and carbanions which determine the gap between pK(R+) and pK(HA) are very sensitive to structural change. (C) 1997 by John Wiley & Sons, Ltd.
The visible-lightphotoredox-catalyzedcarboxylation of benzyl chlorides and bromides with CO2 has been reported. With inexpensive organic dyes as photocatalysts and amines as electron donors, this carboxylation proceeds well in the absence of sensitive organometallic reagents, transition metal catalysts, or metallic reductants. A wide range of commercially available and inexpensive benzyl halides
已经报道了用CO 2对苄基氯和溴进行可见光光氧化还原催化羧化。使用廉价的有机染料作为光催化剂和胺作为电子供体,这种羧化在没有敏感的有机金属试剂、过渡金属催化剂或金属还原剂的情况下进行得很好。范围广泛的可商购且廉价的苄基卤化物经过这种羧化作用以中等至高产率产生有价值的芳基乙酸,包括几种药物分子和药物前体。此外,该反应具有温和的反应条件(1 个大气压的 CO 2和室温)、广泛的底物范围、良好的官能团耐受性、易于扩展和低催化剂负载,从而为芳基乙酸的组装提供了一种有效的方法。
Omega-amino-PEG-phosphoramidites and conjugates thereof
申请人:Chernov K. Boris
公开号:US20060063147A1
公开(公告)日:2006-03-23
ω-Amino-PEG conjugates, and processes and reagents for preparing ω-amino-PEG conjugates are described.
273. Derivatives of 6-aminopenicillanic acid. Part II. Trisubstituted acetyl derivatives
作者:E. G. Brain、F. P. Doyle、K. Hardy、A. A. W. Long、M. D. Mehta、D. Miller、J. H. C. Nayler、M. J. Soulal、E. R. Stove、G. R. Thomas
DOI:10.1039/jr9620001445
日期:——
Triphenylmethylamides (TPMAs): Structure–activity relationship of compounds that induce apoptosis in melanoma cells
作者:Rahul Palchaudhuri、Paul J. Hergenrother
DOI:10.1016/j.bmcl.2008.07.128
日期:2008.11
Triphenylmethylamides (TPMAs) have been previously identified as compounds that arrest cells in the G1-phase of the cell cycle and induce apoptotic death in melanoma cell lines in culture. Here we report the synthesis of a series of TPMA derivatives, allowing the structure-activity relationship of this class of molecules to be established. Several new compounds have been identified that induce death in UACC-62 and SK-MEL-5 human melanoma cell lines, including a compound with enhanced aqueous solubility. (C) 2008 Elsevier Ltd. All rights reserved.