Bicyclic ketones. I. Decomposition of terpene ketone tosylhydrazones

Wheeler, J. W.; Chung, Ryan; Vaishnav, Y.N.; Shroff, C. C.

doi:10.1021/jo01255a013

Cited by 21 publications

(4 citation statements)

References 3 publications

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“…The reduction of the CC double bond of ( R )-umbellulone by catalytic hydrogenation leads to the formation of two diastereoisomers with a clear stereofacial preference for 11 (90% GC) and 12 (10% GC). This catalytic reduction of 10 was studied − , and the stereochemistry of the major compound formed was assigned to 11 . We were able to purify 11 and 12 by medium-pressure chromatography to compare their 1 H and 13 C NMR data.…”

Section: Resultsmentioning

confidence: 99%

Hemisynthesis of Dihydroumbellulols from Umbellulone: New Cooling Compounds

Starkenmann

Cayeux

Brauchli

et al. 2010

J. Agric. Food Chem.

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Although menthol is a common ingredient used in food products, other molecules also evoke coolness through stimulation of the somatosensory system. To discover new molecules having cooling properties, we virtually screened the chemical structures of terpenes and sesquiterpenes to find structures that are similar to (-)-menthol. We realized that dihydroumbellulols could be good candidates. Although their occurrence was reported in Hyptis pectinata Poit, we were unable to obtain these molecules from the plant or to prove their natural occurrence. Therefore, we extracted (-)-(R)-umbellulone from Umbellularia californica Nutt. The (-)-(R)-umbellulone was reduced to prepare (1R,2R/S)-1-isopropyl-4-methylbicyclo[3.1.0]hex-3-en-2-ol, (1R,4R/S)-1-isopropyl-4-methylbicyclo[3.1.0]hexan-2-one, and (1R,2RS,4RS)-1-isopropyl-4-methylbicyclo[3.1.0]hexan-2-ols, named dihydroumbellulols. Sensory analysis suggested that (1R,2R,4S)-dihydroumbellulol has a pleasant, trigeminal cooling effect, about 2-3 times less cooling than (-)-menthol, with a weak odor slightly reminiscent of eucalyptol. In addition, a previously unreported compound was discovered, (-)-(1R)-1-isopropyl-4-methylenebicyclo[3.1.0]hexan-2-one.

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Section: Resultsmentioning

confidence: 99%

Hemisynthesis of Dihydroumbellulols from Umbellulone: New Cooling Compounds

Starkenmann

Cayeux

Brauchli

et al. 2010

J. Agric. Food Chem.

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“…However, attempts to obtain evidence for the proposed carbene intermediate 3 through intermolecular trapping experiments have not been successful, presumably due to the facility of 1,2-C−H insertion. We therefore undertook the synthesis of cycloaddition substrate 25 (Scheme ), which we designed with the expectation that the resulting carbene intermediate 27 in this case would undergo a unique fragmentation process leading to 28 . In the event, thermolysis of 25 affords 28 in 30−35% yield, providing strong evidence in support of our proposed mechanism for the ynone cycloaddition reaction.…”

mentioning

confidence: 90%

Intramolecular [4 + 2] Cycloaddition Reactions of Conjugated Ynones. Formation of Polycyclic Furans via the Generation and Rearrangement of Strained Heterocyclic Allenes

Wills

Danheiser

1998

J. Am. Chem. Soc.

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“…HONO was synthesized by slowly adding a diluted NaNO 2 solution to diluted sulfuric acid [15]. Sabinaketone was previously synthesized by ozonolysis in liquid phase [16]. Ozone was generated by flowing high-purity oxygen through a silent discharge ozonizer (Kaufmann Umwelttechnik, GmBH, Wehr, Germany).…”

Section: Chemicalsmentioning

confidence: 99%

Kinetic and product study of the gas‐phase reaction of sabinaketone with OH radical

Carrasco

Picquet‐Varrault

Doussin

2007

Int J of Chemical Kinetics

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Sabinaketone is one major photooxidation product of sabinene, an important biogenic volatile organic compound. This article provides the first product study and the second rate constant determination of its reaction with OH radicals. Experiments were investigated under controlled conditions for pressure and temperature in the LISA indoor simulation chamber using FTIR spectrometry. Kinetic study was carried out at 295 ± 2 K and atmospheric pressure using the relative rate technique with isoprene as the reference compound. The rate constant was found to be k sabinaketone + OH = (7.1 ± 1.0) × 10 −12 molecule −1 cm 3 s −1 . Acetone and formaldehyde were detected as products of the reaction with the respective yields of R acetone = 0.9 ± 0.2 and R

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Bicyclic ketones. I. Decomposition of terpene ketone tosylhydrazones

Cited by 21 publications

References 3 publications

Hemisynthesis of Dihydroumbellulols from Umbellulone: New Cooling Compounds

Hemisynthesis of Dihydroumbellulols from Umbellulone: New Cooling Compounds

Intramolecular [4 + 2] Cycloaddition Reactions of Conjugated Ynones. Formation of Polycyclic Furans via the Generation and Rearrangement of Strained Heterocyclic Allenes

Kinetic and product study of the gas‐phase reaction of sabinaketone with OH radical

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