Copaiba oil (Copaifera spp.) chemistry and pharmacology

[Alchemica]

The Tropical Plant Database has a good review.

β-Caryophyllene [structure] is a bicyclic hydrocarbon sesquiterpene that occurs in essential oils of many plants. Copaiba oil (Copaifera spp.) seems to be unique with respect to containing high levels of β-Caryophyllene (~50%) in the essential oil.

Copaifera oleoresins are composed of a high amount of hydrocarbon sesquiterpenes, contributing to almost 90% of the total oleoresins composition, followed by a small amount of diterpenes. The main constituent is β-caryophyllene, which is found as one of the most abundant sesquiterpene in copaiba oleoresins [see: Chemistry and biological activities of terpenoids from copaiba (Copaifera spp.) oleoresins]

β-caryophyllene is the main sesquiterpene present in copaiba oil, comprising 40% to 57% of the composition, depending on the Copaifera species [see: Validation of a gas chromatographic method to quantify sesquiterpenes in copaiba oils] Other studies report marked variation in the composition of Copaiba oils and their β-caryophyllene content. In one study, major differences were observed in chemical composition between sources, along with some adulterations [link] Various other factors seem to be important [see: Within plant distribution and emission of sesquiterpenes from Copaifera officinalis]. Copaiba oil from Copaifera officinalis (steam distilled from resin, Brazil) - a common source - potentially requires further batch-specific analysis to confirm its exact composition. β-caryophyllene, α-copaene, and α-humulene appear to be the main chemical markers in Copaifera volatile oils.

TLC (silica gel 60 F254) for β-caryophyllene - Eluent: 2:1 pentane and Et₂O + 1 % HOAc. Visualisation with 5 ml anisaldehyde in 50 ml HOAc + 1 ml conc. H₂SO₄
Rf = ca. 0.80 for terpenes with out functional group, e.g. verticillia- 4(20),7,11-triene, limonene, ß-pinene, α-humulene, ß-caryophyllene etc. (Dark blue/violet)
Rf = ca. 0.50, ß-caryophyllene oxide (Pink spot) [link]

Biological Activity

"Copaifera spp. are used in S. America to produce oleoresin known as 'copaiba', which is taken externally and internally as medicine. Amongst its many curative properties, it is regarded as an aphrodisiac (Plowden 2004)" [The Garden of Eden, S. Voogelbreinder]

A large diversity of studies involving β-caryophyllene, α-copaene, and α-humulene have been reported, demonstrating their high potential as medicines. [link]

"β-caryophyllene was shown to be a selective agonist of the cannabinoid receptor type-2 (CB2) and to exert significant cannabimimetic antiinflammatory effects in mice. Because the widespread plant natural product beta-caryophyllene is an FDA approved food additive and ingested daily with food it is the first dietary cannabinoid. Whether this compound is able to modulate inflammatory processes inhumans via the endocannabinoid system is yet unknown. β-caryophyllene does not bind to the centrally expressed cannabinoid receptor type-1 (CB1) and therefore does not exert psychomimetic effects."[wiki]

"β-caryophyllene is a putative candidate as the main anti-inflammatory compound. In vitro studies suggest that β-caryophyllene is a dietary cannabinoid with important anti-inflammatory effects through the cannabinoid type-2 (CB(2)) receptor. In vitro, this plant sesquiterpene binds selectively to CB(2) receptor inhibiting proinflammatory pathways, including toll-like receptor complex CD14/TLR4/MD2, which normally leads to the expression of IL-1β, IL-6, IL-8, and TNF-α . In vivo, oral treatment with β-caryophyllene decreases inflammation in a mouse model of colitis. It is possible that that a downstream mechanism of β-caryophyllene might be the decrease of TNF-α release by inhibition of CB-2 cannabinoid receptor. In addition, other sesquiterpenes may be involved on the mechanisms underlying the anti-inflammatory effects. α-humulene, another sesquiterpene present, reduces eosinophil recruitment and release of several proinnflammatory substances in an experimental model of airways allergic inflammation or following LPS injection in the rat paw. It is possible that different sesquiterpenes interact synergistically contributing to the anti-inflammatory effects observed." [link]

A variety of biological activities have been uncovered, including analgesic [1], neuroprotective [2], CB2 receptor mediated anxiolytic & antidepressant [3], anti-alcoholism [4], immunomodulatory and anti-inflammatory activity [5]. Numerous other studies have revealed antioxidant, anti-cancer, anti-allergic, anti-plasmodial, antimicrobial, insecticidal activity, amongst others.

Whilst ingestion of small quantites of copaiba oil is generally considered to be safe, β-caryophyllene is liable to autooxidation if exposed to air, leading to the formation of a known sensitiser:

"β-Caryophyllene started to oxidize immediately when air exposed and after 5 weeks almost 50% of the original compound was consumed. Caryophyllene oxide was found to be the major oxidation product. Hydroperoxides of β-caryophyllene could not be detected in the oxidation mixture. Caryophyllene oxide was shown to be an allergen of moderate strength and β-caryophyllene air exposed for 10 weeks showed a weak sensitizing capacity" [link]

Anecdotally (amazon.com), one user reports effective relief of back pain (previously medicated with hydrocodone) with a "00 size capsule of this [copaiba oil] twice a day" and another (for general arthritic pain) with oral doses of "10 drops per day", in combination with other essential oils. The Tropical Plant Database gives doses of 5-15 drops, 2-3 times daily

Does anyone else have experiences to share?

Edited July 24, 2014 by Alchemica
updated