109-75-1Relevant articles and documents
THERMAL DEGRADATION OF GLUCOSINOLATES
Macleod, Alexander J.,Panesar, Satwinder S.,Gil, Victor
, p. 977 - 980 (1981)
Three glucosinolates (allyl-, benzyl- and 2-phenethyl-) were shown to degrade thermally in a GC column to yield products identical with those obtained conventionally on enzymic decomposition, namely nitriles and isothiocyanates.Nitriles were formed more readily at 125 deg but the facility for isothiocyanate production varied slightly with the glucosinolate; 2-phenethylglucosinolate was the most labile of those studied yielding isothiocyanate at a column temperature of 150 deg.Temperature was confirmed as the cause of degradation by isolated heated-tube experiments.The results have significance both with regard to analytical methodology for glucosinolates and their products, and with regard to furthering understanding of the mechanisms of glucosinolate degradation.Key Word Index- Criciferae; glucosinolates; nitriles; isothiocyanates; thermal degradation.
Overtone-induced isomerization of allyl isocyanide
Segall, Jeffrey,Zare, Richard N.
, p. 5704 - 5714 (1988)
The rate of isomerization of allyl isocyanide to allyl cyanide is monitored using Stern-Volmer kinetics when various features of the 5-O and 6-O C-H overtone stretch region are excited.Previously, Reddy and Berry found that the isomerization rates varied from band to band and that the variations were not monotonic with excitation energy.They attributed this behavior to nonstatistical effects.It is found in this study that the isomerization rates vary within an overtone band by up to a factor of 1.8, in addition to the variations from band to band seen previously.This observation rules out the possibility that the overtone bands are purely lifetime broadened.In addition, the photoisomerization rate increases with increasing temperature.An increase of 60 K increases the photolysis yield in the 5-O C-H region by a factor of 3-4, while increases in the 6-O C-H region are smaller, 25percent-60percent.These effects can be qualitatively explained if the overtone spectrum of allyl isocyanide is inhomogeneously broadened because of the presence of vibrational "hot bands." In this case, molecules excited by the photolysis laser will have varying amounts of initial thermal energy depending on where the laser is tuned within a band.A simple model for the effects of hot bands on the isomerization rate is in good agreement with experimental results.It is not necessary to invoke nonstatistical effects in order to explain the observed overtone-pumped isomerization rates of allyl isocyanide.
A method for the cyanation of alkenes using nitromethane as a source of cyano group mediated by proton-exchanged montmorillonite
Motokura, Ken,Matsunaga, Kenta,Miyaji, Akimitsu,Yamaguchi, Sho,Baba, Toshihide
, p. 7034 - 7038 (2014)
A novel method for the cyanation of alkenes using nitromethane as a source of the cyano group is described. H+-montmorillonite mediates the cyanation through the in situ formation of trimethylsilanecarbonitrile oxide from nitromethane and allylsilane, followed by 1,3-dipolar cycloaddition and subsequent rearrangement to afford the corresponding nitriles.
Copper-Catalyzed Carbonylative Synthesis of β-Homoprolines from N-Fluoro-sulfonamides
Wu, Xiao-Feng,Yin, Zhiping,Zhang, Youcan
supporting information, p. 1889 - 1893 (2020/03/24)
A new methodology for the carbonylative transformation of N-fluoro-sulfonamides into N-sulfonyl-β-homoproline esters has been described. In the presence of a catalytic amount of Cu(OTf)2, a range of β-homoproline derivatives were prepared in moderate to good yield. The reaction proceeds via the intramolecular cyclization and intermolecular carbonylation of a free carbon radical. Notably, this procedure offers the possibility to build potential functionalized bioactive molecules.
Metal-free highly regioselective aminotrifluoroacetoxylation of alkenes
Lovick, Helena M.,Michael, Forrest E.
supporting information; experimental part, p. 1249 - 1251 (2010/04/01)
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