Organic mass spectrometry II. The electron impact fragmentation of dimedone and 2-ethyldimedone

Goto, Toshio; Tatematsu, Akira; Nakajima, Yasuo; Tsuyama, Hitoshi

doi:10.1016/s0040-4039(01)83980-0

Cited by 11 publications

(9 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Basic investigations have been carried out by Vandewalle et al (15,16), whereas Goto et al (17) and Maquestiau and Lejeune (18) focused on spectra of dimedone derivatives. Therefore, it appeared highly desirable to better understand the mass spectrometric fragmentation pattern of chiloglottone1 and its analogs to identify respective diagnostic ions and, thus, facilitate structure elucidation of other volatiles representing this new type of compound in nature.…”

mentioning

confidence: 99%

The discovery of 2,5-dialkylcyclohexan-1,3-diones as a new class of natural products

Franke

Ibarra

Schulz

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

Orchids employing sexual deceit attract males of their pollinator species through specific volatile signals that mimic female-released sex pheromones. One of these signals proved to be 2-ethyl-5-propylcyclohexan-1,3-dione (chiloglottone1), a new natural product that was shown to be most important in the relations between orchids of the genus Chiloglottis, native to Australia, and corresponding pollinator species. Systematic investigations on the mass spectrometric fragmentation pattern of 2,5-dialkylcyclohexan-1,3-diones identified key ions providing information about the structures of the substituents at positions 2 and 5. Results enabled us to identify 2-ethyl-5-pentylcyclohexan-1,3-dione (chiloglottone2) and 2-butyl-5-methylcyclohexan-1,3-dione (chiloglottone3) as new natural products that play a decisive role in the pollination syndrome of some Chiloglottis species. During field bioassays, pure synthetic samples of chiloglottone1-3 or mixtures thereof proved to be attractive to the corresponding orchid pollinators. Because of their likely biogenesis from ubiquitous fatty acid precursors, 2,5-dialkylcyclohexan-1,3-diones may represent a hitherto overlooked, widespread class of natural products.2-butyl-5-methylcyclohexan-1,3-dione ͉ 2-ethyl-5-pentylcyclohexan-1,3-dione ͉ Chiloglottis ͉ semiochemical ͉ mass spectrometry

show abstract

mentioning

confidence: 99%

The discovery of 2,5-dialkylcyclohexan-1,3-diones as a new class of natural products

Franke

Ibarra

Schulz

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

show abstract

“…111 (25) 125 (14) 128 (19) 139 (1) -125 (14) 128 (20) 139 (1) -125 ( 8 ) 139 (2) 139 (2) 139 (15) 139 (15) - n/e 59…”

Section: (100)unclassified

Studies in organic mass spectrometry. XVII The fragmentation of methyl enol ethers of 1,3‐cyclohexanediones and 1,3‐cyclopentanediones

Cant

Maenhaut-Claeys

Francque

et al. 1974

Bulletin des Soc Chimique

View full text Add to dashboard Cite

thyl enol ethers of 1,3-cyclohexanediones and 1,3-cyclopentanediones is studied. Six membered rino; compounds behave quite straithforwardly and in accordance with the fragmentation suggested f o r 1,3-cyclohexanediones in the enol form. Some fragmentations are supported by deuterium labelling. tuted isomers display identical spectra. This isomerisation is studied by metastable transitions, low energy spectra and deuterium labelling; a possible mechanism is advanced.The influence of alkyl substituents on the mass spectral behaviour of meIn the case of enol ethers of 1,3-~yclopentanediones the 4-or 5-substi-The mass spectral behaviour of acyclic 1,3-diones1 to 4, 1,3-~yclohexane-diones5 to and 1,3-cycl~pentanediones~ has already been discussed. It could be proven that both tautomeric forms display different fragmentation patterns.It is therefore of interest to investigate corresponding enol ethers. The fragmentation behaviour of some enol derivatives of dirnedone'l and acyclic 1,3-diketones" has been published.ethers of alkyl substituted 1,3-cyclohexanediones and 1,3-cyclopentanediones.It appears, as well from the published data as from the present work that the most important ions are formed by initial cleavage 0 to the carbonyl function.The fragmentation of the cyclic enol ethers is discussed in function of the length and the position of the alkyl substituent; the mechanisms are in all cases, supported by high resolution measurements.We now present the fragmentation of methyl en01 I; R = H 11; R = Et 111; R = n.Pr IV; R = n.Bu).Holder of a bursary of V; R = Et VIII; R = Me VI; R = n.Pr IX; R = n.Pr VII; R = n.Bu X; R = n.Bu C. Van

show abstract

“…THE MASS spectral behaviour of acyclic 1,3-dione~l*~*~ and 1,3-cyclohe~anediones~ to 7 has already been discussed. From examination of the spectra it could be deduced that both tautomeric forms are present in the gas phase and that enol-and diketomolecular ions display different fragmentation patterns.…”

mentioning

confidence: 99%

Studies in organic mass spectrometry—IX: The fragmentation of alkylsubstituted 1,3‐cyclopentanediones

Cant

Vandewalle

1971

Org. Mass Spectrom.

View full text Add to dashboard Cite

The mass spectra of 2-and 4-substituted 1,3-~yclopentanediones are discussed. Methyl substituted compounds display mostly ring degradation, while for longer alkyl groups fragmentations in the side chain are responsible for most of the total ionization. As was found for other 1,3-diketones the spectra of 1,3-~yclopentanediones show typical and separate fragmentations for both diketoand enol-molecular ions.

show abstract

Organic mass spectrometry II. The electron impact fragmentation of dimedone and 2-ethyldimedone

Cited by 11 publications

References 1 publication

The discovery of 2,5-dialkylcyclohexan-1,3-diones as a new class of natural products

The discovery of 2,5-dialkylcyclohexan-1,3-diones as a new class of natural products

Studies in organic mass spectrometry. XVII The fragmentation of methyl enol ethers of 1,3‐cyclohexanediones and 1,3‐cyclopentanediones

Studies in organic mass spectrometry—IX: The fragmentation of alkylsubstituted 1,3‐cyclopentanediones

Contact Info

Product

Resources

About