29785-41-9Relevant articles and documents
Catalysis of the Photo-Fries Reaction: Antibody-Mediated Stabilization of High Energy States
Dickerson, Tobin J.,Tremblay, Martin R.,Hoffman, Timothy Z.,Ruiz, Diana I.,Janda, Kim D.
, p. 15395 - 15401 (2007/10/03)
A conformationally constrained hapten is presented that is capable of catalyzing the first antibody-mediated photo-Fries rearrangement. In this reaction, absorption of light energy by a diphenyl ether substrate results in homolytic C-O bond cleavage followed by recombination to yield biphenyl-derived products. The most proficient antibody studied converts 4-phenoxyaniline 15 into 2-hydroxy-5-aminobiphenyl 16 under high-intensity irradiation at a rate of 8.6 μM/min. These results support a recent hypothesis stating that immunization with conformationally constrained haptens provides higher titers for the acquisition of simple binding antibodies; however, in this case, conformational constraint does not ensure the development of more efficient catalysts. Using the obtained antibodies, the presence of products resulting from escape of free radicals from the solvent cage can be suppressed, altering the excited state energy surface such that free radicals are funneled into the formation of the desired biphenyl product. However, studies also show the inactivation of the antibodies as a result of photodecay of the biphenyl product. Using an isocyanate scavenging resin, the photodecay product could be removed and the inactivation of the antibody drastically reduced. Furthermore, despite the observed photodecay, turnover of the antibody was present; this represents the first case in which true turnover of a photochemical reaction using a catalytic antibody could be observed.
The Electrochemical Preparation and Kinetic and Product Studies of Acylated Quinol and Quinol Ether Imines. In Search of the Hydrolysis Products of the "Ultimate" Carcinogen of N-Acetyl-2-aminofluorene
Novak, Michael,Helmick, John S.,Oberlies, Nicholas,Rangappa, Kanchugarakoppal S.,Clark, William M.,Swenton, John S.
, p. 867 - 878 (2007/10/02)
The N-acetyl and benzoyl derivatives of 4-methoxy-4-phenyl-2,5-cyclohexadienone imine and the N-benzoyl derivative of 4-hydroxy-4-phenyl-2,5-cyclohexadienone imine (1a-c) have been prepared via anodic oxidation of the corresponding amide of 4-aminobiphenyl in either methanol or water/ acetonitrile, respectively.The products and the kinetics of the acidic and basic hydrolyses of these compounds were studied and the results compared with other N-acylquinol imine derivatives, including N-acetyl-4-hydroxy-4-phenyl-2,5-cyclohexadienone imine (1d), generated by solvolytic routes.The chemistry of these compounds was dependent upon the pH and the substituents on the quinol imine derivative.The major reaction pathways were hydrolysis of the imine linkage to afford the respective dienone and phenyl migration to afford the amides of 2-hydroxy- or 2-methoxy-5-aminobiphenyl.The reactivity of the quinol imine derivatives follows the order: 4-hydroxyl more reactive than 4-methoxyl compounds and N-acetyl more reactive than N-benzoyl derivatives.The higher reactivity for the former compounds is attributed to the greater electron-donating ability of the 4-hydroxyl versus the 4-methoxyl group.The higher reactivity of the N-acetyl relative to the N-benzoyl derivatives is attributed to the ca. 30-fold increase in basicity of the N-acetyl functionality.The additive effect of the 4-hydroxyl and N-acetyl functionality on the basic quinol imine moiety makes compounds having both of the groups difficult to isolate in aqueous media.This serves as a limitation for the preparation of the quinol imine derivative of N-acetyl-2-aminofluorene via the anodic oxidation methods reported herein.
Synthesis and antifilarial activity of N-[4-[[4-alkoxy-3-[(dialkylamino)methyl]phenyl]amino]-2-pyrimidinyl]-N'-ph enylguanidines
Angelo,Ortwine,Worth,Werbel,McCall
, p. 1258 - 1267 (2007/10/02)
A series of N-[4-[[4-alkoxy-3-[(dialkylamino)methyl]phenyl]amino]-2-pyrimidinyl]-N' -phenylguanidines have been synthesized for antifilarial evaluation. Reaction of the appropriate benzenamines with N-cyanoguanidine, followed by condensation of the result
