6857-93-8Relevant articles and documents
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Barfield,M.,Brown,S.E.,Canada,E.D.
, p. 3355 (1980)
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Viola,A.,Iorio,E.J.
, p. 856 - 858 (1970)
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Influence of the chemical structure on odor qualities and odor thresholds in homologous series of alka-1,5-dien-3-ones, alk-1-en-3-ones, alka-1,5-dien-3-ols, and alk-1-en-3-ols
Lorber, Katja,Schieberle, Peter,Buettner, Andrea
, p. 1025 - 1031 (2015/04/22)
Odor qualities and odor thresholds in air in homologous series of synthesized alk-1-en-3-ols and alka-1,5-dien-3-ols and their corresponding ketones were evaluated by gas chromatography-olfactometry. In the series of the alk-1-en-3-ols and alk-1-en-3-ones the odor quality changed successively from pungent for the compounds with five carbon atoms via metallic, vegetable-like for the six- and seven-carbon odorants to mushroom-like for the compounds with eight and nine carbon atoms. With further increase in chain length the mushroom-like impression decreased and changed to citrus-like, soapy, or herb-like. In both series, two odor threshold minima were found for the six-carbon and also for the eight- and nine-carbon odorants, respectively. In contrast to this, the odor qualities in the series of the (Z)- and (E)-alka-1,5-dien-3-ols and their corresponding ketones did not change significantly with geranium-like, metallic odors and an increasing mushroom-like odor note with increasing chain length. The lowest thresholds were found for the eight- and nine-carbon (Z)-compounds, respectively.
Rearrangement of Substituted Bicyclohex-2-yl Mesylates Under Solvolytic Conditions
Della, Ernest W.,Elsey, Gordon M.,Skouroumounis, George
, p. 1231 - 1244 (2007/10/02)
When heated in formic acid, methyl 2-mesyloxybicyclohexane-2-carboxylate (3) ionizes significantly faster than expected and yields the rearranged isomer (6) essentially quantitatively.The latter, on the other hand, solvolyses at a much reduced rate.These data are interpreted as evidnce for the presence in the ester of a favourable mesomeric interaction which largely offsets an otherwise destabillizing inductive effect when the ester is attached to a carbocationic centre.The corresponding cyano mesylates (8) and (29) were found to behave in an analogous manner when exposed to the solvolytic conditions.Heating the related acid mesylate (25) in an aqueous medium leads to the 1,2 hydroxy acid (24), whereas its sodium salt (26) is considerably more reactive and gives the 2,2-hydroxy acid (11).These observations are rationalized on the basis of the greatly enhanced ability of the COO- group relative to a COOH to stabilize an adjacent positively charged centre.The methyl substituent is also found to exert a profound effect on the nature of the solvolysis products, in hot formic acid, for example, 1-methylbicyclohex-2-yl mesylate (31) produces the formate (32) in which the substitution pattern is retained.Under milder conditions, however, the ester (31) solvolyses with rearrangement to give the 2,2-formate (33).
