<oai_dc:dc xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:oai_dc="http://www.openarchives.org/OAI/2.0/oai_dc/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xsi:schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd">
  <dc:creator>Gaplovsky M</dc:creator>
  <dc:creator>Il'ichev YV</dc:creator>
  <dc:creator>Kamdzhilov Y</dc:creator>
  <dc:creator>Kombarova SV</dc:creator>
  <dc:creator>Mac M</dc:creator>
  <dc:creator>Schwörer MA</dc:creator>
  <dc:creator>Wirz J</dc:creator>
  <dc:date>2005</dc:date>
  <dc:description xmlns:ns0="xml" ns0:lang="en">Irradiation of 2-nitrobenzyl alcohol (1, R = H) and 1-(2-nitrophenyl)ethanol (1, R = Me) in various solvents yields 2-nitroso benzaldehyde (4, R = H) and 2-nitroso acetophenone (4 R = Me), respectively, with quantum yields of about 60%. The mechanism of this reaction, known since 1918, was investigated using laser flash photolysis, time-resolved infrared spectroscopy (TRIR), and 18O-labeling experiments. The primary aci-nitro photoproducts 2 react by two competing paths. The balance between the two depends on the reaction medium. Reaction via hydrated nitroso compounds 3 formed by proton transfer prevails in aprotic solvents and in aqueous acid and base. In water, pH 3-8, the classical mechanism of cyclization to benzisoxazolidine intermediates 5, followed by ring opening to carbonyl hydrates 6, predominates. The transient intermediates 3 and 6 were identified by TRIR. Potential energy surfaces for these reactions were mapped by density functional calculations.</dc:description>
  <dc:identifier>https://sonar.ch/global/documents/288159</dc:identifier>
  <dc:language>eng</dc:language>
  <dc:relation>info:eu-repo/semantics/altIdentifier/doi/10.1039/b409927c</dc:relation>
  <dc:relation>info:eu-repo/semantics/altIdentifier/pmid/15616689</dc:relation>
  <dc:source>Photochemical &amp; photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology. - 2005</dc:source>
  <dc:subject xmlns:ns1="xml" ns1:lang="en">Benzyl Alcohols</dc:subject>
  <dc:subject xmlns:ns2="xml" ns2:lang="en">Hydrogen-Ion Concentration</dc:subject>
  <dc:subject xmlns:ns3="xml" ns3:lang="en">Lasers</dc:subject>
  <dc:subject xmlns:ns4="xml" ns4:lang="en">Molecular Structure</dc:subject>
  <dc:subject xmlns:ns5="xml" ns5:lang="en">Nitrobenzenes</dc:subject>
  <dc:subject xmlns:ns6="xml" ns6:lang="en">Nitroso Compounds</dc:subject>
  <dc:subject xmlns:ns7="xml" ns7:lang="en">Photochemistry</dc:subject>
  <dc:subject xmlns:ns8="xml" ns8:lang="en">Photolysis</dc:subject>
  <dc:subject xmlns:ns9="xml" ns9:lang="en">Protons</dc:subject>
  <dc:subject xmlns:ns10="xml" ns10:lang="en">Quantum Theory</dc:subject>
  <dc:subject xmlns:ns11="xml" ns11:lang="en">Spectrophotometry, Infrared</dc:subject>
  <dc:subject xmlns:ns12="xml" ns12:lang="en">Ultraviolet Rays</dc:subject>
  <dc:title xmlns:ns13="xml" ns13:lang="en">Photochemical reaction mechanisms of 2-nitrobenzyl compounds: 2-nitrobenzyl alcohols form 2-nitroso hydrates by dual proton transfer.</dc:title>
  <dc:type>http://purl.org/coar/resource_type/c_6501</dc:type>
</oai_dc:dc>