ABSTRACT
The synthesis of various new trialkylhydroxylamines is described. The rate constant of the C-O bond cleavage of these new alkoxyamines has been measured. For example, C-O bond homolysis rates in a series of para-substituted TEMPO-styryl compounds TEMPO-CH(CH3)C6H5X 1a (p-MeO), 1b (p-Me), 1d (p-H), 1e (p-Br), and 1f (p-MeO2C) are presented. Furthermore, rate constants for the C-O bond cleavage of alpha-heteroaryl-substituted secondary alkoxyamines are discussed. A correlation by which the rate constant for the C-O bond cleavage of TEMPO-derived alkoxyamines can be predicted from the C-H BDEs of the corresponding alkanes is presented. Solvent effects as well as the effect of camphorsulfonic acid on the rate of the C-O bond homolysis are discussed. Finally, EPR and kinetic evidence show that alkoxyamines derived from nitroxides which are capable of intramolecular H-bonding undergo C-O bond cleavage faster than the corresponding non-H-bond-forming analogues.
Subject(s)
Extremities/injuries , Frostbite/diagnosis , Adolescent , Adult , Chronic Disease , Humans , Male , Middle AgedSubject(s)
Blood , Chronic Kidney Disease-Mineral and Bone Disorder/blood , Ultrafiltration , Adult , Aged , Alkaline Phosphatase/blood , Calcium/blood , Chronic Kidney Disease-Mineral and Bone Disorder/pathology , Female , Humans , Male , Middle Aged , Parathyroid Hormone/blood , Phosphates/blood , Renal Dialysis/adverse effectsABSTRACT
The most significant problem in recognizing workplace hazards is the lack of adequate surveillance systems for the identification and assessment of harmful exposures.
