Photorelease of alcohols from 2-nitrobenzyl ethers proceeds via hemiacetals and may be further retarded by buffers intercepting the primary aci-nitro intermediates

Journal of the American Chemical Society

Volumn 127, Issue 25, 2005, Pages 8934-8935

  Hellrung, Bruno ^a   Kamdzhilov, Yavor ^a   Schwörer, Markus ^a   Wirz, Jakob ^a  

^a UNIVERSITY OF BASEL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

1,3 DIOXOLANE DERIVATIVE; 2 NITROBENZYL ETHER; 2 NITROSOBENZALDEHYDE; ALCOHOL; ALDEHYDE DERIVATIVE; BUFFER; DIOXOLANONE; ETHER DERIVATIVE; GLYCOLIC ACID; METHANOL; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; ARTICLE; CHEMICAL STRUCTURE; INFRARED SPECTROMETRY; LASER; NONHUMAN; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PH; PHOTOLYSIS; SPECTROPHOTOMETER; TIME;

ACETALS; ALCOHOLS; BUFFERS; ETHERS; HYDROGEN-ION CONCENTRATION; MOLECULAR STRUCTURE; NITRO COMPOUNDS; NITROBENZENES; PHOTOLYSIS;

EID: 21244477774     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052300s     Document Type: Article

References (10)

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5. Supporting Information.
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8. a (I = 0.1 M. 25°C) of methoxyacetic acid is 3.5; Headley, A. D.; Starnes, S. D.; Wilson, L. Y.; Famini, F. G. J. Org. Chem. 1994, 59, 8040-8046.
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10. A fraction of the glucose might be released directly from intermediate B, B → 2 + D-glc. This shortcut could be favored by the steric bulk of D-glc. Whether alcohol release from 2-nitroveratryl ethers also proceeds via long-lived hemiacetal intermediates is not known, but the frequently adopted assumption that the release rate is equal to the decay rate of the readily observable aci-nitro transients is clearly not safe at this point.