Diterpenes, acid

Schlosser s super base 615 f. Schmidt trichloroacetimidate glyco-sidation 528,531,537,556 Schwartz s reagent 606, 616 scopadulcic acid A 571 scopadulcic acid diterpenes 569 secocorrin 100, 122, 126 f., 130... 

Moose Aloes aloes Scotch pine Pinifolic acid (diterpene). 

Both fatty and resin acids (diterpene acids) are obtained as a by-product of the pulping of wood for paper. The mixture is known as tall oil. The separated resin acids are known as rosin. Resin acids such as abietic acid (12.20) can also be obtained as exudates of pine trees. 

Cassanes.— -Caesalpin (41), from Caesalpinia pulcherrima, possesses the cassane skeleton, and is thus related to the bitter principles isolated from the seeds of Caesalpinia bonducella. Cassminic acid is a minor constituent of the bark of Erythrophleum guineense. Spectroscopic measurements and an interrelationship with cassane-16,19-dioic acid have established " it as 6-oxo-7-hydroxycass-13-ene-16,19-dioic acid. N.m.r. measurements and bromination-dehydrobromina-tion studies are in accord with the axial 14a-configuration now accepted for the cassamic acid diterpenes. 

The condensable category consists of components such as fatty acids, resin acids, diterpenes, and triterpenes. Although... 

The antioxidant activity of rosemary has been well documented over the past 50 years. The active constituents include phenolic acids, diterpenes, and flavonoids. Cuppett and HaU (1998), Ho et al. (2000) and Yanishlieva and Heinonen (2(X)1) have completed thorough reviews on rosemary antioxidants, and readers should consult these for additional information. Three prominent compounds - camosic acid, camosol, and rosmarinic acid (Figure 3) - have received the most attention. Camosic acid and camosol account for 1.7-5.5%... 

The isoprene unit exists extensively in nature. It is found in terpenes, camphors, diterpenes (eg, abietic acid), vitamins A and K, chlorophyll, and other compounds isolated from animal and plant materials. The correct stmctural formula for isoprene was first proposed in 1884 (7). 

Dlterpenes. Diterpenes contain 20 carbon atoms. The resin acids and Vitamin A are the most commercially important group of diterpenes. GibbereUic acid [77-06-5] (110), produced commercially by fermentation processes, is used as a growth promoter for plants, especially seedlings. 

Wood is the raw material of the naval stores iadustry (77). Naval stores, so named because of their importance to the wooden ships of past centuries, consist of rosin (diterpene resin acids), turpentine (monoterpene hydrocarbons), and associated chemicals derived from pine (see Terpenoids). These were obtained by wounding the tree to yield pine gum, but the high labor costs have substantially reduced this production in the United States. Another source of rosin and turpentine is through extraction of old pine stumps, but this is a nonrenewable resource and this iadustry is in decline. The most important source of naval stores is spent sulfate pulpiag Hquors from kraft pulpiag of pine. In 1995, U.S. production of rosin from all sources was estimated at under 300,000 metric tons and of turpentine at 70,000 metric tons. Distillation of tall oil provides, in addition to rosin, nearly 128,000 metric tons of tall oil fatty acids annually (78). 

Chemistry of rosin. All three types of rosin consist primarily of C20 mono-carboxylic diterpene resin acids, the most common of which have the molecular formula C20H20O2. In addition, rosins contain small amounts of neutral and other acidic components (e.g. fatty acids in tall oil rosin). The neutral components of rosins are diterpene alcohols, hydrocarbons and aldehydes, and their contents generally vary between 5 and 15 wt%. 

Fig. 7. Principal nionocarboxylic diterpene acids skeletons in rosins. Dotted line indicates that the chemical group is located below plane (see p. 266 in 118]).

The assumption of these conjugated double bonds makes possible a tetracyclic nucleus which accords with the suggestion previously made by the authors that these alkaloids might be structurally related to the diterpenes. It may also be noted that one of the nitric acid oxidation products of pseudaconitine has been recorded as unexpectedly giving a pyrrole reaction on destructive distillation. ... 

The exchange of aromatic protons can be effected in the absence of any -OH or —NH2 activating group during the course of a Clemmensen reduction in deuteriochloric and deuterioacetic acid mixture (see section Ill-D). This reaction has been carried out with various tricyclic diterpenes and is best illustrated by the conversion of dehydroabietic acid into its 12,14-d2-labeled analog (40 -+ 41).Amalgamated zinc is reportedly necessary for the exchange reaction since the results are less satisfactory when a zinc chloride-mercuric chloride mixture is used. 

The TMM [4-1-3] cycloaddition to pyrone has been employed in a synthetic study of a novel biologically active diterpene pseudolaric acid B (106), in which the formation of the bridged adduct (107) from the 2-pyrone (108) is the key step in the sequence (Scheme 2.29). A mixture of the other isomer (109) and the methylenecyclopentane (110) was also isolated from the reaction. It is important to point out that the presence of a tin co-catalyst is critical in effecting the reaction. This is the first example a "tin-effect observed in a [4-1-3] cycloaddition [40]. 

Carboxylative TMM q cloaddition has also been realized with 3-methoxytropone and precursor (56) to produce an epimeric mixture of acids (122), which was employed in a synthetic study of the bicyclic diterpene sanadaol (123). The use of bi-dentate ligand tpdp (12) and high pressure did not improve the reaction. However, the addition of MesSnOAc as a co-catalyst did produce a better yield of (122) (Scheme 2.33) [16]. 

For the performance of an enantioselective synthesis, it is of advantage when an asymmetric catalyst can be employed instead of a chiral reagent or auxiliary in stoichiometric amounts. The valuable enantiomerically pure substance is then required in small amounts only. For the Fleck reaction, catalytically active asymmetric substances have been developed. An illustrative example is the synthesis of the tricyclic compound 17, which represents a versatile synthetic intermediate for the synthesis of diterpenes. Instead of an aryl halide, a trifluoromethanesul-fonic acid arylester (ArOTf) 16 is used as the starting material. With the use of the / -enantiomer of 2,2 -Z7w-(diphenylphosphino)-l,F-binaphthyl ((R)-BINAP) as catalyst, the Heck reaction becomes regio- and face-selective. The reaction occurs preferentially at the trisubstituted double bond b, leading to the tricyclic product 17 with 95% ee. °... 

Provided that the silanolate elimination proceeds with anti selectivity, it must be concluded, that the intermediate homoallylic alcohol has an anti configuration, and thus the reagent has an ( -configuration. Acidic hydrolysis of the enol ether leads to enones the overall sequence consists of a nucleophilic acroylation. This has also been applied in the total synthesis of the marine diterpene ( )-aplysin-2067. 

The first total synthesis of the marine dolabellane diterpene (+)-4,5-deoxy-neodolabelline (70) was accomplished by D. R. Williams et al. [58]. The trans-disubstituted dihydropyran moiety in key intermediate 69 was efficiently prepared from mixed acetal 66 by RCM with second-generation catalyst C and subsequent Lewis acid-catalyzed allylation of ethyl glycosides 67 with allylsi-lane 68 (Scheme 12) [59]. 

Diels-Alder reaction of the furan derivative 148 with homochiral bicyclic enone 149 is the key step [56] in the total synthesis of the diterpenes jatropho-lone A and B, 151 and 152, respectively, isolated from Jatropha gossypiifolia L [57], Initial efforts to carry out the cycloaddition between 148 and 149 under thermal or Lewis-acid conditions failed due to diene instability. Application of 5kbar of pressure to a neat 1 1 mixture of diene and dienophile afforded crystalline 150 with the desired regiochemistry (Scheme 5.23). Subsequent aromatization, introduction of the methylene group, oxidation and methylation afforded (-l-)-jatropholones 151 and 152. 

Studies on the bitterness of other compoundsdo not, however, support this model. The bitter amino acids and sugars, for example, do not possess an AH,B unit of this dimension. As already mentioned, there is some evidence suggesting that there is more than one type of bitter-taste quality and receptor. If this is the case the diterpenes probably interact with a receptor showing a steric requirement difierent from that involved with the other classes of compounds. 

The GC-MS data (Figure 16.11) of the violet zone of B. carterii revealed that the unchanged diterpenes (verticillatriene, cembrene A, and cembrene C) and the nortriterpenes with carbohydrate structure originated from the pyrolyzed triterpenes (Figure 16.12) of the a- and (3-boswellic acids, named 24-norursa-3,12-diene (compound 7), 24-norursa-3,9(ll),12-triene (compound 8), 24-noroleana-3,12-diene (compound 9), and 24-noroleana-3,9(ll),12-triene (compound 10). 

The effect of flavonoids on spore germination and hyphal growth of ecto-mycorrhizal fungi is poorly known. However, several metabolites relea.sed by the plant roots trigger events leading to their infection (44,55). In the saprotrophic phase, spores of several ectomycorrhizal fungi respond to stimulation by abietic acid, the diterpene resin acid, in root exudates (56). 

We focused our attention on Tall oil, a by-product of the paper industry, whenever this is prepared according to the KRAFT process. Said material consists of a mixture of highly unsaturated fatty acids (many of which with conjugated diene systems) and terpene derived rosin acids. The rosin acids have the molecular formula C20H30O2 and thus belong to the diterpenes (pimaric and abietic acids). Tall Oil has an iodine number equal to approximately 170 gl2/100 g. 

One of the most significant differences between Arabica and Robusta coffees is in the caffeine content. Robusta coffees contain almost twice the caffeine found in Arabica coffees. There are some other differences recognized thus far Robustas contain almost no sucrose and only very small amounts of the kaurane and furokaurane-type diterpenes they contain higher proportions of phenols, complex carbohydrates (both soluble and hydrolyzable), volatile fatty acids on roasting, and sulfur compounds, all in comparison with Arabicas. References to these distinctions can be found in Chapter 6 of this book. 

Methods for the decaffeination of green coffee beans, mainly with solvents after a steaming, have already been described. Even with the selective adsorption techniques to remove only caffeine, it is unlikely that the full character of the starting beans can be realized in a final decaffeinated beverage the result is that Robusta coffees are generally used to prepare decaffeinated coffee. The cost is kept down and the treatment, anyway, reduces any harsh or bitter flavor that the Robusta coffee may have had. The resulting beverage will be relatively caffeine-free, but Robusta coffee will contribute more soluble carbohydrates, phenols, and volatile fatty acids, and much less of the diterpenes found in Arabica coffees. 

The plant is used to treat leprosy the roots are used to heal ulcers and to cure ringworm infection. A decoction of the leaves is drunk to treat tuberculosis and to improve general weakness. In Cambodia, Laos, and Vietnam, an infusion of the bark is used to correct nervous affections. The plant is known to elaborate lupane triter-pene saponins and kaurane diterpenes including 16-aH, 17-isovalerate-ent-kauran-19-oic acid, which strongly inhibited the enzymatic activity of cyclooxygenase in vitro (76,77). 

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