<b>The Cyclization of Geranic Acids. Preparation of a Cyclobutanone</b>

Beereboom, John J.

doi:10.1021/ja00904a067

Cited by 26 publications

(9 citation statements)

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“…pulegium has been reported as being a chemical polymorph species, both in qualitative and/or quantitative composition. A correlation has been established between oil composition and origin for 38 Greek populations of M. pulegium. [8] M. spicata plants with essential oils rich in piperitenone and piperitone epoxides are the most common chemotype found in Greek wild populations, as shown here.…”

Section: Resultsmentioning

confidence: 99%

“…Piperitenone (4) was prepared as previously reported. [38] Purity of the isolated product (97.3%) was estimated according to GC/MS analysis. Its structural characterization (included as Supplementary Information) was carried out by mass spectral analysis and NMR experiments and the results were in agreement with previous reports.…”

Section: Essential Oils and Pure Compounds Analysis By Gas Chromatogrmentioning

confidence: 99%

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Biocidal Compounds from Mentha sp. Essential Oils and Their Structure–Activity Relationships

Kimbaris

González-Coloma⊥

Andrés

et al. 2017

Chemistry & Biodiversity

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Essential oils from Greek Mentha species showed different chemical compositions for two populations of M. pulegium, characterized by piperitone and pulegone. Mentha spicata essential oil was characterized by endocyclic piperitenone epoxide, piperitone epoxide, and carvone. The bioactivities of these essential oils and their components have been tested against insect pests (Leptinotarsa decemlineata, Spodoptera littoralis and Myzus persicae), root-knot nematodes (Meloydogine javanica) and plants (Lactuca sativa, Lolium perenne, Solanum lycopersicum). The structure-activity relationships of these compounds have been studied including semi-synthetic endocyclic trans-carvone epoxide, exocyclic carvone epoxide, a new exocyclic piperitenone epoxide and trans-pulegone epoxide. Leptinotarsa decemlineata feeding was affected by piperitenone and piperitone epoxide. Spodoptera littoralis was affected by piperitone epoxide and pulegone. The strongest nematicidal agent was piperitenone epoxide, followed by piperitone epoxide, piperitenone and carvone. Germination of S. lycopersicum and L. perenne was significantly affected by piperitenone epoxide. This compound and carvone epoxide inhibited L. perenne root and leaf growth. Piperitenone epoxide also inhibited the root growth of S. lycopersicum. The presence of a C(1) epoxide resulted in strong antifeedant, nematicidal and phytotoxic compounds regardless of the C(4) substituent. New natural crop protectants could be developed through appropriate structural modifications in the p-menthane skeleton.

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Section: Resultsmentioning

confidence: 99%

Section: Essential Oils and Pure Compounds Analysis By Gas Chromatogrmentioning

confidence: 99%

Biocidal Compounds from Mentha sp. Essential Oils and Their Structure–Activity Relationships

Kimbaris

González-Coloma⊥

Andrés

et al. 2017

Chemistry & Biodiversity

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“…~ Als Kandidat fur die Umwandlung in ( i ) -Filifolon schien uns das Keten-thioacetal 12 besonders geeignet, da beide notwendigen Schritte, nanilich die hydrogenolytische Spaltung von C,S-Bindungen und die partielle Hydrierung eines konjugierten Diens prinzipiell rnit Raney -Ni [22] moglich sind. Tatsiichlich entstand bei der Behandlung von 12 rnit Raney-Ni W2 [23] in Aceton [24] 52% (*)-1 (Schema 3), dessen Eigenschaften rnit denen friiher beschriebener Praparate [2] [5] identisch waren. Daneben fanden wir im Produkt noch 5 bzw.…”

Section: Synthese Von (And)-filifolon ((And)-l)unclassified

“…8% der (f)-Dihydrofilifolone 16 und 17 (vgl. [2]). (6)); 7,17 (dd, J = 3,2, 1,5, IH, H-C(3)); 639 (dd, J = 4,5, 1.5, lH, H-C(5)); 6,41 (ddd, J = 4 3 , 3,2, 0,8, IH, H-C(4)); 3,48 (sept., J = 7, lH, (CH,),CH); 3,38, 3.28 (2s, je 3H, (CH,),N); 1,15 (d, J = 7, 6H, (CH,),CH).…”

Section: Synthese Von (And)-filifolon ((And)-l)mentioning

confidence: 99%

“…-Filifolon (S), ein Monoterpen mit einem Bicyclo[3.2.0]heptan-Gerust, kommt in der Natur in beiden enantiomeren Formen vor, das (1 R,SR)-Isomere in Ziera smithii ANDREW aus Australien und das (lS,SS)-Isomere in Artemisia jZijiiliu TORREY, einer Sandsalbei aus Arizona [l]. Synthetisch ist 1 bisher mittels Ac,O und NaOAc [2] aus Geraniumsiiure (2), durch Photolyse aus Verbenon (3) [3], durch saurekatalysierte Umlagerung aus Chrysanthenon (4) [4] und durch Cyclisierung aus Ocimenon (5) [5] und aus dem Diazoketon 6 [6] zuganglich geworden (Schema I).…”

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Addition von Dimethylketen an 6‐heterosubstituierte Fulvene. Synthese von (±)‐Filifolon

Stadler

Rey

Dreiding

1984

Helvetica Chimica Acta

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Summary[2 + 2]Cycloaddition of dimethylketene to 6-ethoxy-(8) and 6,6-(tetramethylenedithio)fulvene (9) gave the 4-alkylidenebicyclo[3.2.0]heptenones 11 and 12, respectively. Under the same conditions, 6-(dimethylamino)fulvene (7) was acylated to yield the push-pull fulvene 10. Raney-Ni reduction converted the adduct 12 into the monoterpene (*)-filifolone ((&)-l, 52%) and minor amounts of the four related ketones 1 4 1 7 . Cycloaddition of a second dimethylketene to the primary cycloadduct 1 l a yielded the cis,transoid,cis-tricyclic diketone 13.

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Ketene Cycloadditions

1994

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The reaction of ketene with itself was described almost simultaneously in 1908 by Chick and Wilsmore in England, and by Staudinger and Klever in Germany; priority for the discovery was attributed to Wilsmore by the German group. Ketene cycloaddition was an early example of a peculiar process, one that formed carbon–carbon bonds with ease, often without the need for solvent, catalyst, or high heat. Subsequent work by others was done in the shadow of Staudinger's exhaustive and rigorous study of all phases of ketene reactivity. Three factors led to a resurgence of interest in this reaction beginning in the 1960s. Haloketenes, which had previously eluded study, were found to have high reactivity, and the halogens could easily be removed after the reaction. The increasing sophistication of powerful analytical methods, particularly nuclear magnetic resonance spectroscopy, led to discovery of the interesting stereochemical aspects of this reaction. Finally, the new theory of orbital symmetry conservation provided a conceptual framework to rationalize these puzzling “no mechanism” reactions. This chapter is a review of cycloaddition reactions of ketenes. Here, a cycloaddition is defined as a reaction of a ketene with an unsaturated organic compound to give a cyclic product by a mechanism that, in principle, involves the almost simultaneous formation of two bonds between two reactants. While there is no concern here as to whether bond formation is concerted or stepwise, no other chemical process can take place between the formation of the first and second bond. Definition here involves both structural and mechanistic factors, and it is difficult to avoid a certain amount of arbitrariness. Products, such as dehydroacetic acid, which seem to us to arise by concatenation of ketene molecules followed by cyclization are excluded. These reactions, are more properly considered to arise from a series of ionic reactions, and the prediction of the eventual product does not take advantage of the special mechanistic features commonly associated with true cycloadditions. Additions to imines to give β‐lactams are numerous and will be covered in a separate review. The literature has been searched to the end of 1988. Many reviews devoted partially or exclusively to ketene cycloadditions have been published. Specific topics that have been reviewed include haloketenes, fluoroketenes, cyanoketenes, intramolecular cycloadditions, conjugated ketenes, and β‐lactam antibiotics. Ancillary topics pertinent to ketene cycloadditions that have been reviewed include cycloreversion reactions, ketene equivalents, which provide ketene functionality with olefin‐like reactivity especially in [4 + 2] reactions, application of frontier molecular orbital theory to cycloadditions, and a critical discussion of cycloadditions with polar intermediates. Applications of cyclobutanones in synthesis have also been reviewed.

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The Cyclization of Geranic Acids. Preparation of a Cyclobutanone

Cited by 26 publications

References 1 publication

Biocidal Compounds from Mentha sp. Essential Oils and Their Structure–Activity Relationships

Biocidal Compounds from Mentha sp. Essential Oils and Their Structure–Activity Relationships

Addition von Dimethylketen an 6‐heterosubstituierte Fulvene. Synthese von (±)‐Filifolon

Ketene Cycloadditions

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