Oxidation of Terpenes with Molecular Oxygen. I. Oxidation of Terpinolene in Aqueous Dispersion<sup>1</sup>

Borglin, J. N.; Lister, D. A.; Lorand, E. J.; Reese, Johannes

doi:10.1021/ja01166a072

Cited by 11 publications

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“…In later experiments a modified Erlenmeyer flask was employed to provide a greater surface area for oxidative attack, and the water was added directly to the substrate. [Similar techniques using aqueous dispersions have been reported by Borglin et nl (5)].…”

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confidence: 57%

THE OXIDATION OF TERPENES. I. MECHANISM and REACTION PRODUCTS OF D‐LIMONENE AUTOXIDATION

Bernhard

Marr

1960

Journal of Food Science

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The deterioration of essential oils and products containing essential oils has been a serious problem in the food flavor and essential oil fields for many years. A study of terpene autoxidation would give a more thorough understanding of the reactions occurring between the terpene, oxygen, and the catalyst. Although these reactions are known to be quite complex (2, 4, 5. 6, 7, 13, 14, 15, 16, 18, 19), involving initiation of a free radical chain reaction, chain propagation with oxygen participation, and chain termination, a systematic study of several of the more important variables would help clarify some of the more cryptic aspects of the over-all problem. The natural choice for a substrate is limonene since this terpene is one of the most widely distributed and abundant hydrocarbons found in the plant kingdom. It occurs in numerous volatile oils and is present in some as the main constituent, especially in the citrus oils. n-Limonene has been identified in oil of orange (about 90% ), lemon, mandarin, lime, grapefruit, bergamot, neroli, petitgrain, elemi, caraway (400/o), dill, fennel, celery (60%)) erigeron, and orthodon (8).EXPERIMENTAL The course of the autoxidation reactions was followed by oxygen uptake which was determined by conventional techniques using a Warburg respirometer (17). The main compartment of the reaction flask contained 0.2 ml (1.23 x lo4 moles) of n-limonene unless otherwise noted, and the center well of the vessel contained 0.2 ml of distilled water. It was found to be extremely difficult to obtain accurate and meaningful readings of the manometers when the oxidations were carried out in the absence of water. This is probably due to some anomalous effects of vapor pressure encountered between the water in the manometer fluid and the substrate. In later experiments a modified Erlenmeyer flask was employed to provide a greater surface area for oxidative attack, and the water was added directly to the substrate. [Similar techniques using aqueous dispersions have been reported by Borglin et nl (5)].The authors were unable to distinguish any difference between oxidations carried out in the two flasks. All autoxidation experiments were conducted in duplicate, and frequently a number of replicate determinations were carried out. A control experiment was run concurrently with all manometric examinations.The control vessel contained all the constituents of the actual reaction mixtures examined with the exception that an inert gas, nitrogen, filled the vessel instead of air.The gas-liquid chromatographic apparatus employed to separate the products of the autoxidation of n-limonene was an Aerograph mode1 A-90-C.b Columns were constructed of stainless steel tubing, g inch o.d. and 10 feet in length.The support material used throughout this study was Sil-0-Cel C-22 diatromaceous earth firebrick (30-60 mesh). Fractions of this were sieved to size and further graded by sedimentation in water, after which they were dried at 110" C for 17 hr. The liquid phase was introduced by deposition from benzene so...

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confidence: 57%

THE OXIDATION OF TERPENES. I. MECHANISM and REACTION PRODUCTS OF D‐LIMONENE AUTOXIDATION

Bernhard

Marr

1960

Journal of Food Science

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“…While mere terpenic hydrocarbons are not soluble in water, oxygenated derivatives were shown to partly pass into the water phase upon distillation, most likely owed to the capacity to form hydrogen bonds (Rajeswara Rao and others ; Edris ). Moreover, Borglin and others () as well as Mercier and others () reported that terpenes became water‐soluble upon oxidation. Chapard and others () observed the same effect in oxidized essential oils.…”

Section: Analysis Of Essential Oilsmentioning

confidence: 94%

“…Accordingly, initially formed oxidation products from terpenoids, assigned as hydroperoxides, were reported to decompose in the presence of light, heat, or upon increasing acidity (Hellerström and others ; Blakeway and others ; Hagvall and others ). Borglin and others () observed that peroxidic products resulting from oxidation of the monoterpene terpinolene degraded promptly, even at room temperature.…”

Section: Alterations Of Essential Oils and Possible Consequencesmentioning

confidence: 99%

“…Chapard and others () observed the same effect in oxidized essential oils. Less stable hydroperoxides and epoxides, formed as intermediates, were suggested to be hydrolyzed into terpenic polyols in the presence of water (Borglin and others ; Lorand and Reese ). As a consequence, polar, conductive, and/or acidic secondary products accumulated during terpenoid degradation and subsequently passing into the water phase, might be captured by combined conductivity and pH measurements.…”

Section: Analysis Of Essential Oilsmentioning

confidence: 99%

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Stability of Essential Oils: A Review

Turek

Stintzing

2013

Comp Rev Food Sci Food Safe

937

565

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In recent years, consumers have developed an ever-increasing interest in natural products as alternatives for artificial additives or pharmacologically relevant agents. Among them, essential oils have gained great popularity in the food, cosmetic, as well as the pharmaceutical industries. Constituting an array of many lipophilic and highly volatile components derived from a great range of different chemical classes, essential oils are known to be susceptible to conversion and degradation reactions. Oxidative and polymerization processes may result in a loss of quality and pharmacological properties. Despite their relevance for consumers, there is a paucity of information available addressing this issue. Therefore, the present review provides a comprehensive summary on possible changes in essential oils and factors affecting their stability. Focusing on individual essential oils, the various paths of degradation upon exposure to extrinsic parameters are outlined. Especially temperature, light, and oxygen availability are recognized to have a crucial impact on essential oil integrity. Finally, analytical methods to assess both genuine as well as altered essential oil profiles are evaluated with respect to their suitability to track chemical alterations. It is believed that only a careful inspection of essential oils by a set of convenient methods allows profound quality assessment that is relevant to producers and consumers alike.

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“…Both of these positions are of the allyl type and susceptible to oxygen attack. Borglin et al 18 who studied the air oxidation of terpinolene remarked that "oxygen reacts with terpinolene more readily than with other common terpenes". Borglin et al 18 also found that a complex mixture of terpenoid alcohols were formed by the oxidation (not possible to resolve and identify in 1950).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Cooked Carrot Volatiles. AEDA and Odor Activity Comparisons. Identification of Linden Ether as an Important Aroma Component

Buttery

Takeoka

2013

J. Agric. Food Chem.

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MS with GC-RI evidence was found for the presence of linden ether in cooked carrot (Daucus carota). Evaluation of the GC effluent from cooked carrot volatiles using aroma extract dilution analysis (AEDA) found linden ether with the highest flavor dilution (FD) factor. Others with 10-fold lower FD factors were β-ionone, eugenol, the previously unidentified β-damascenone, (E)-2-nonenal, octanal (+ myrcene), and heptanal. All other previously identified volatiles showed lower FD factors. Odor thresholds, concentrations, and odor activity values of previously identified compounds are reviewed. This indicated that at least 20 compounds occur in cooked carrots above their odor thresholds (in water). Compounds showing the highest odor activity values included β-damascenone, (E)-2-nonenal, (E,E)-2,4-decadienal, β-ionone, octanal, (E)-2-decenal, eugenol, and p-vinylguaiacol.

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Oxidation of Terpenes with Molecular Oxygen. I. Oxidation of Terpinolene in Aqueous Dispersion¹

Cited by 11 publications

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THE OXIDATION OF TERPENES. I. MECHANISM and REACTION PRODUCTS OF D‐LIMONENE AUTOXIDATION

THE OXIDATION OF TERPENES. I. MECHANISM and REACTION PRODUCTS OF D‐LIMONENE AUTOXIDATION

Stability of Essential Oils: A Review

Cooked Carrot Volatiles. AEDA and Odor Activity Comparisons. Identification of Linden Ether as an Important Aroma Component

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Oxidation of Terpenes with Molecular Oxygen. I. Oxidation of Terpinolene in Aqueous Dispersion1

Cited by 11 publications

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THE OXIDATION OF TERPENES. I. MECHANISM and REACTION PRODUCTS OF D‐LIMONENE AUTOXIDATION

THE OXIDATION OF TERPENES. I. MECHANISM and REACTION PRODUCTS OF D‐LIMONENE AUTOXIDATION

Stability of Essential Oils: A Review

Cooked Carrot Volatiles. AEDA and Odor Activity Comparisons. Identification of Linden Ether as an Important Aroma Component

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Oxidation of Terpenes with Molecular Oxygen. I. Oxidation of Terpinolene in Aqueous Dispersion¹