Of -P-eudesmol

FIGURE 20.51 Biotransformation of p eudesmol (157) and y-eudesmol (157a) by Gibberella suabinetii. 

Noma, Y, T. Etashimoto, S. Kato, and Y. Asakawa, 1997. Biotransformation of (+)-p-eudesmol by Aspergillus niger. Pmc. 41st TEAC 224—226. 

In addition to ( )-valerane, a wide variety of other sesquiterpenes, including ( )-ishwarane, ( )-ish-warone, ° copaene, ylangene, ( )-seychellene ( )-sativene, ( )-longifoline, " ( )-copa-camphene," ( )-damsin," ( )-A < >-capnellene, ( )-pentalenene, (-)-P-vetivone" and ( )-P-eudesmol have been synthesized by pathways involving cycloalkylation of saturated ketone enolates. 

This class of compounds may be found in essential oils extracted with both polar solvents and non-polar solvents. The structure of a sesquiterpene alcohol, newly isolated from the oil extracted from the wood of Amyris balsamifera (Rutaceae), has been reported [76]. These investigators either identified by GC-MS or isolated a total of 23 sesquiterpenoids, including valerianol (23) (21.5% of oil), 1-epi-a-eudesmol (24) (10.7%), 10-e/ i -y-eudesmol (25) (9.7%), elemol (26) (9.1%), P-eudesmol (27) (7.9%), y-eudesmol (28) (6.6%), a-eudesmol (29) (4.8%) and P-sesquiphellandrene (30) (4.7%) as the major constituents. 7-... 

Nine eudesmane derived sesquiterpenes were isolated from Aristolochia species. Among them, a- and P- eudesmols (325), (326), a-, P- and 8- selmenes (319), (322), (321) and selina-3,7(ll)-diene (320) were found in the essential oils of various Aristolochia members. Govindachari et al. [334] isolated aristolochene (324), a sesquiterpene... 

Given the relatively rare occurrence of eremophilanes in Eremophila species, it is perhaps of little surprise that compounds displaying the putative precursor skeleton, eudesmane, have also been rarely observed. P-Eudesmol (71) has been isolated or detected in a number of species, sometimes co-occurring with elemol (72) (14,15,67). 

Atractylodes lancea rhizome and aconite root are paeoniflorin, glycyrrhizin, P-eudesmol, and aconitine, respectively. Each compound plays a complementary role, having different mechanisms of action. Their mechanisms in combined (blend) effects of paired or triplet combinations of these compounds have been investigated, and the rationality of the traditional combined medicines has been elucidated. The neuromuscular blocking actions have been compared by using skeletal muscle in vitro and in situ, and in normal and diseased states. 

In an early study with Teucrium polium [76] a sesquiterpene P-eudesmol (141) was isolated together with a group of amino acids. 

The GC/MS analysis of the volatile oil of T. polium [79] showed that sesquiterpenoids comprise the major part of the oil (78.6 %), certain sesquiterpene alcohols such as P-eudesmol and a-cadinol.Two new sesquiterpene diols 7-ej7/-eudesm-4(15)-ene-ip, 6a-diol (146) and 7-epi-eudesm-4(15)-ene-ip, 6P-diol (147) were isolated and their structures were elucidated by H and NMR spectral analyses. 

Three agaroflirans (85-87) and P-eudesmol (88) were isolated from the petroleum ether-soluble fraction of the methanolic extract of the fresh rhizomes of A. japonica [63]. It is biogenetically interesting that P-eudesmol was present in the same plant with agaroflirans which possess a 10-epieudesmol skeleton. From the rhizomes of A. japonica, three eudesmane-type sesquiterpenes, 10-ep/-5P-hydroperoxy-p-eudesmol (89), 10-e /-5a-hydroperoxy-P-eudesmol (90) and 4,10-e/ /-5P-hydroxydihydroeudesmol (91) were isolated and their structure were determined by spectroscopic methods and chemical conversions [64]. Compounds 89-91 are considered to be biosynthesized from lO-ep/ -y-eudesmol (92), which was a possible precursor of agarofuran-type... 

Well-known eudesmane derivatives in flavors and fragrances include a- and p-selinene from the oils of Cannabis saliva var. indica (Moraceae), celery (Apium graeveolens, Umbelliferae) and hops (Humulus lupulus, Moraceae), (+)-a- and (+)-P-eudesmol from some oils of eucalyptus (Eucalyplus macarlhuri), (-)-epi-y-eudesmol with its woody odor from the north African oil of geranium (Pelargonium odoralissimum and allied species), and the almost odorless diastereomeric (+)-y-eudesmol from various ethereal oils (+)-p-Costus acid and (+)-p-costol belong to the constituents of the essential oil obtained from the roots of Saussurea... 

Only a few volatile sesquiterpenes presenting important central activities are currently known. P-Eudesmol (34) was found to be one of the volatile active principles of the Chinese medicinal herb Atractylodes lancea DC. (Asteraceae) with alleged antagonist properties useful in intoxication by anticholinesterase agents of the organophosphorus type (Chiou et al. 1997). Experimental data show that p-eudesmol (34) prevents convulsions and lethality induced by electroshock but not those induced by PTZ or picrotoxin (Chiou et al. 1995). With a very similar chemical structure. 

Chiou, L. C., Ling, J. Y., and Chang, C. C. 1995. p Eudesmol as an antidote for intoxication from organophos-phorus anticholinesterase agents. European Journal of Pharmacology 292 151-156. 

The stereoisomeric farnesols have been similarly investigated [300]. These possess juvenile hormone activity [225, 226] and could be detected thin-layer chromatographically as the sexual attractant of the male bumble bee [269, 270]. The chromatography was carried out with benzene-ethyl acetate (95 + 5) on silica gel V- and szial gel 47-layers (Firm 114) [303, 309]. The trans4rans-ia,mesol (hi / 27) then lay below the as- mns-farnesol (hi / 36). This sequence remains also when pure benzene is used for development [304] and is observed with the farnesol esters too [307—309]. Seikel and Rowe [237] have studied the TLC of the eudesmols. They separated milligram amounts of a- and p-eudesmol with benzene-petroleum ether (50 + 50) on alumina layers, 500 (xm thick. The use of ascending technique is said to augment the differences in the hi /-values. 

FIGURE 15.50 Biotransformation of a-eudesmol (153) and p-endesmol (157) by Aspergillus niger and Aspergillus cellulosae. 

P-Eudesmol, isolated from So-jutsu (Atmctylodis lanceae rhizomas), a perennial growing to the height of about Im and widely used in traditional Chinese medicine, is known to have various unique effects on the nervous system. 

The pattern of substitution of both P-eudesmol and a-santonin can be accounted for by assuming that the cyclization of farnesyl diphosphate, followed by (or preceded by) suitable oxidation changes at allylic positions, is as shown in Scheme 11.50. 

Scheme 11.50. A cartoon representation of the organization of farnesyl diphosphate that, on oxidation and cyclization (or cyclization and oxidation), produces both P-eudesmol and a-santonin.

Major components of the oil are d- mo-nene (ca. 60%) and other limonene-type terpenes4selinene (ca. 10%), and about 3% phthalides. Other constituents include santa-lol, a- and P-eudesmol, dihydrocarvone, and fatty acids (linoleic, palmitic, petroselinic, stearic, oleic acids, etc.), among others (jiangsu ... 

The bark of C. burmanii yields 1.32% oil containing 1,8-cineole (51.4%), a-terpineol (12.5%), camphor (9.0%), terpinen-4-ol (8.5%), bomeol (1.8%), a-pinene (1.6%), P-caryophyllene (1.6%), /i-cymene (1.0%), and lesser amounts of myristicin, a-humulene, P-eudesmol, and others. The leaf oil contains mostly 1,8-cineole (28.5%) andbor-neol (16.5%) with lesser amounts of a-terpineol (6.4%), -cymene (6.1%), spathulenol (5.8%), terpinen-4-ol (4.1%), P-caryophyl-lene (2.9%), and others. Eugenol is absent in both the bark and leaf oils (ravindran). 

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