- Copper-Catalyzed Redox Deacylation of Isomeric N- and O-Benzoylhydroxylamines
-
N- and O-benzoylhydroxylamines are, in principle, capable of forming five-membered metal chelates structurally similar to those of α-amino esters.Because α-amino esters are hydrolyzed by many metal ions, the metal-promoted or -catalyzed reactions of N- and O-benzoylhydroxylamines were examined.Two metals that are active with α-amino esters - Ni(II) and Zn(II) - show no reaction with either benzohydroxamic acid or O-benzoylhydroxylamine in aqueous solution.Cu(II) accelerates the rate of benzoic acid formation with both compounds by factors of up to 60- and 40-fold, respectively, under the conditions evaluated.Both reactions give benzoic acid as product, but hydroxylamine is not a product in either reaction.We observe that O-benzoylhydroxylamine reacts with Cu(II) with net oxidation and with Cu(I) with net reduction of the nitrogenous product.When a substoichiometric amount of Cu(II) is used, copper serves as a catalyst to effect deacylation with redox disproportionation of the starting material.
- Wathen, Steven P.,Czarnik, Anthony W.
-
p. 6129 - 6133
(2007/10/02)
-
- -AZOXYBIS(METHYLENE) BIS(3-CHLOROBENZOATE): POTENT MUTAGEN FROM REACTION OF HEXAMETHYLPHOSPHORAMIDE, N-METHYLHYDROXYLAMINE AND -NITROSOMETHANE DIMER WITH 3-CHLOROPEROXYBENZOIC ACID
-
-Azoxybis(methylene) bis(3-chlorobenzoate), an exceptionally potent mutagen (3050 revertants/nmol) in the Salmonella typhimurium (strain TA100) assay, is formed in trace (-nitrosomethane dimer on treatment of hexamethylphosphoramide or N-methylhydroxylamine with 3-chloroperoxybenzoic acid.
- Kimmel, Ella C.,Holden, Ian,Segall, Yoffi,Casida, John E.
-
p. 2819 - 2820
(2007/10/02)
-
- Photochemical Studies of Nitromethane in Solution. III. Nitromethane in Isopropyl Alcohol
-
Photolysis of nitromethane in isopropyl alcohol solution at λ = 254 nm and λ >/= 290 nm has been investigated.In the reaction mixture besides the products found by other authors 2-hydroxy-2-propyl azodioxymethane and pinacol have also been found.Quantum yields of some photoproducts formation have been determined.The photochemical reaction of cis and trans nitrosomethane dimers, probably the main products in the investigated system, have been examined in isopropanol alcohol solution at 254 nm and 313 nm.The reaction mechanism has been proposed and discussed.
- Kozubek, Halina,Paszyc, Stefan
-
p. 481 - 488
(2007/10/02)
-