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Eight terpenoid derivatives with juvenile hormone activity were tested for teratogenicity. Three of the derivatives were teratogenic when administered to mice as a single intraperitoneal injection of 1 mg/gm on either day 9 or day 10 of pregnancy. However, intubation at 5 mg/gm of the two most teratogenic derivatives resulted in one of the derivatives marginally increasing the incidence of abnormal embryos above peanut oil-intubated controls; the other intubated derivative was without adverse affect. Of the remaining five compounds, two with high juvenile hormone activity were without teratogenic effect when injected at 1 mg/gm. Since teratogenic effects were observed only at a dose above likely exposure levels and by a route of administration not possible in the environment, support is provided for the potential use of terpenoid derivatives in the control of insect pests.

Examination of fragmentation patterns of five bicyclic ketones containing cyclopropane rings and their deuterated analogs indicates that similarity in structure gives minimal similarity in fragmentation. No generalizations can be made concerning either the loss of similar fragments or their deuterium content.

As a continuation of our study on the biogenetically patterned transformation leading to the natural terpenoids, conversion of an eudesmanolide directing to the related eremophilanolide was investigated and the object was accomplished. After several attempts, treatment of 5α, 6α-epoxy-dihydroalantolactone (15) with HCOOH-acetone (1 : 2) at reflux was found to afford eight products (A-H). Among them, two major products (products A and B) and one minor product (product D), which were obtained in a combined yield of 46%, were elucidated to be the desired eremophilanolides (17, 18, and 23) on the basis of the physicochemical evidence and the chemical conversion of 23 to tetrahydroligularenolide (34). The structure of the product C was assigned 20 on the basis of its physical properties and the chemical derivation. Afterwards, a better reaction condition transforming 15 to give 17 and 18 in a combined 68% yield was found.

Gas chromatography of leaf and twig extracts from a provenance test revealed seven principal monoterpenes. Tissues differed in relative quantity for six monoterpenes; provenances differed for six monoterpenes from leaves, and all monoterpenes from twigs. All of the six compounds except 3-carene were present in all samples. Cluster analysis subdivided the species range into eastern and western clusters bordering at about 80 °W Long. Within-cluster variation was greater in the eastern grouping. Four monoterpenes from leaves and all monoterpenes from twigs followed the east–west pattern. The illustrated pattern of geographic variation complemented results of other studies.

Chloroplastsisolated in organic solvents (“non-aqueous chloroplasts”)incorporate [2-14C]-mevalonate into geranylgeraniol and phytoene. No incorporation into phytol or into other carotenoids was achieved, even in mixtures of non-aqueous chloroplasts with chloroplasts prepared in aqueous media. The incorporation of geranylgeranyl pyrophosphate into phytoene by the non-aqueous chloroplast preparation has been demonstrated, and the stereochemistry of hydrogen loss in phytoene synthesis by non-aqueous chloroplasts has been determined.

The isoprenoid alkanes present in a seep oil from Costa Rica have been examined using gas chromatography and mass spectrometry. In addition to the predominance of the C 16 and C 18 -C 20 regular isoprenoid alkanes, the C 21 and C 23 -C 25 regular isoprenoid alkanes were identified. The C 26 , C 28 and C 30 regular isoprenoid alkanes were tentatively identified. No evidence for the regular C 17 , C 22 or C 27 isoprenoid alkanes was found. The compounds 3,7,11- trimethyltetradecane and 3,7,11-trimethylhexadecane were tentatively identified. It is suggested that a higher regular isoprenoid structure (or structures) is required in addition to phytol to account for the distribution of isoprenoid alkanes.

Mycobacterium fortuitum utilises 2,6,10,14-tetramethylpentadecane (pristane) as the sole carbon source. Products isolated from the bacterial lipids included 2,6,10,14-tetramethylpentadecan-1-o1, 2,6,10,14-tetramethylpentadecanoic acid and 4,8,12-trimethyltridecanoic acid. The isolation of only the 2(RS),6(S),10(S) isomers of the C 19 alcohol and acid respectively, and of the 4(S),8(S) isomer of the C 16 , acid, from oxidation of the 6(R),10(S) isomer of pristane, indicate attack at only one terminus of this substrate. When a mixture of the 6(R),10(S); 6(R),10(R); and 6(S),10(S) isomers (2:1:1) of pristane was utilised, the 6(R),10(S) isomer was preferentially oxidised.

The mass spectra of six compounds belonging to the class of terpenoid coumarins and of four of their deuterium analogs have been studied. Decomposition pathways for these substances under the action of electron impact have been suggested. It has been shown that from the mass spectra of compounds of this series it is possible to determine their molecular weights and, in atomic mass units, the weights of their terpene moieties, and also to establish the presence of hydroxy and acyloxy groups in the bicyclic terpene moiety.

Microorganisms capable of utilizing pristane (2,6,10,14-tetramethylpentadecane) as a sole source of carbon and energy were isolated from soil specimens. A strain BPM 1613, tentatively classified in the genus Nocardia, accumulated several oxidation products of pristane in the culture fluid. Silica gel chromatography of the ethyl ether extract from the culture fluid yielded pristanol and pristanic acid as major products and pristyl pristanate and pristyl aldehyde as minor products. The confirmations on the estimated structures of these oxidation products are described in detail.

—The incorporation of [2-14C]mevalonate into nonsaponifiable lipids by rat brain homogenates is inhibited by phenolic acids derived from tyrosine. The phenyl acids derived from phenylalanine are inhibitory only at very high concentrations compared with phenolic acids. The brain is more sensitive to inhibition by the phenolic acids than the liver. These studies indicate a possible role for phenolic acids in the impairment of cerebral sterol metabolism in phenylketonuria.

From the heartwood of Pterocarpus santalinus a group of six closely related sesquiterpenes has been isolated which includes three new sesquiterpenes namely isopterocarpolone, pterocarptriol and pterocarpdiolone besides the known β-eudesmol, pterocarpol and cryptomeridiol. Their structures have been determined by spectral and chemical studies. Three triterpenes, acetyl oleanolic aldehyde, acetyl oleanolic acid, and an unidentified compound along with pterostilbene have also been obtained.

Sorghum plants that had been subjected to different degrees of water stress were examined for the occurrence of endogenous compounds capable of inducing stomatal closure, i.e. "antitranspirants". Acidic extracts contained increased amounts of abscisic acid (ABA) as the amount of stress increased, but another highly active compound easily distinguished from ABA also accumulated. This compound, also found in neutral extracts, was probably all trans-farnesol, an isoprenoid alcohol which, like ABA, is a sesquiterpenoid. Highly dilute solutions of "commercial" farnesol induced stomatal closure when applied to isolated epidermis of Commelina.

On the basis of chemical and spectroscopic evidence, the structure and absolute configuration of lasiokaurinol isolated from Isodon lasiocarpus (HAYATA) KUDO were established as ent-1β-acetoxy-7β, 20-epoxy-16-kaurene-6α, 7α, 14α, 15α-tetraol (9). The structure of another minor diterpenoid, lasiokaurinin, was proposed as 10 on the basis of spectroscopic evidence. Some chemical reactions confirmed its structure and relative stereochemistry as 10.

Methods for the detailed analysis of diterpenoid metabolites from Gibberella fujikuroi are described. The metabolites from 2-[3H]-mevalonic acid lactone are separated by partition chromatography on Sephadex LH20 columns, detected by radio-counting and characterised by gas-chromatography directly linked to radio-counting and MS. From one fermentation, 72 compounds were detected. Of these, 25 known diterpenes, including 15 gibberellins, were identified and 7 new products were assigned tentative structures.

Two structurally related sesquiterpenoid metabolites, complicatie acid and hirsutic acid C, have been produced separately as the principal terpenoid metabolic products in stirred fermentations of Stereum complicatum (Fr.) Fr. in which the pH value was, respectively, controlled at 5·0 or allowed to fall to 2·4. The identity of complicatie acid with both hirsutic acid N and ramealin, uncharacterized fungal metabolites first observed more than 25 years previously and (including hirsutic acid C) since unobtainable, is suggested. These metabolites have the same ‘hirsutane’ carbon skeleton as the coriolin group of basidiomycete sesquiterpenes.

A study has been made of the principal rearrangement products resulting from formic acid treatment of 19-hydroxy-ent-beyerene epoxide (3). In concentrated solutions 3 has been found to undergo a deep seated rearrangement to the allylic alcohol (14). A mechanism for the formation of 14 is proposed involving a novel 1,4-hydride shift in the bicyclo[3:2:1]octane C/D ring system following cleavage of the C15O bond. Supporting evidence has been obtained from a study of the specifically labelled epoxide (4), the deuterium in 14 appearing exclusively at C12. Four products (7 and 11–13) emanating from the known beyerane → kaurane interconversion have been identified.

The relative amounts of chlorophyll, leucine, α-alanine and α-ketoisocaproic acid in tea leaves, and those of carotenoids, β-ionone, dihydroactinidiolide, theaspirone, β-amyrin, acetate, trans-2-hexenal and phenlacetaldehyde in processed black tea have been found to vary with climatic conditions, and indicate the mechanism of flavour development in tea. These variations are related to the degree of CO 2 fixation, and the extent of intra- as compared with extra- chloroplastidic biosynthetic reactions. Evidence is discussed that extra-chloroplastidic biogenesis of terpenoid compounds from leucine leads to the development of tea flavour, whereas intrachloroplastidic fixation of CO 2 , and the consequent derivation of terpenoids from acetate results in the production of teas without flavour. The leucine pathway for terpenoid biogenesis operates in conditions of climatic stress which limit CO 2 fixtation in the leaf, whereas the acetate pathway predominates in conditions of vigorous growth.

From the roots ofFerula mogoltavica, two new terpenoid coumarins have been isolated — mogoltavidin and mogoltavicin — and also one known one — gummosin.

The novel nor-sesquiterpenoids, the davanafurans, have been isolated from the oil of Artemisia pallens, the principal component being the cis, threo-isomer (1a). The absolute configuration of this isomer, and the relative stereochemistry of the other isomers, have been established by synthesis from linalool oxides of known configuration.

The biosynthesis of dehydrotremetone in Eupatorium rugosum has been investigated by feeding radioactive precursors to intact plants. The carbon atoms of acetate-[1- 14 C] and acetate-[2- 14 C] were identified in dehydrotremetone by degradation of the molecule. From the pattern of labeling it was concluded that the acetophenone moiety was derived from acetate via the polyacetate pathway. From the incorporation of mevalonate it appeared that the furan ring and its side chain were formed from an isoprenoid compound. Potential aromatic intermediates were chemically synthesized and also fed to plants but only tremetone was found to be efficiently incorporated into dehydrotremetone. Neither 4-hydroxyacetophenone nor 4-hydroxy-3[isopenten-(2)-yl]-acetophenone were efficiently incorporated into dehydrotremetone.

A regular C 25 isoprenoid alkane (2,6,10,14,18-pentamethyleicosane) has been isolated from highly saline Tertiary sediments. The isolation utilized elution chromatography, urea adduction and gas chromatography; identification was based on the mass spectrum. This C 25 isoprenoid may represent a biological marker, possibly typical for a lagoonal-type, saline environment.

In addition to 6-hydroxy- and 6,18-dihydroxy-(—)-kaurenes, fromStachys silvatica L. (family Labiatae) we have isolated a new diterpenoid of the kaurane series which we have called stachysic acid and for it we have established the structure of 6β-acetoxy-(—)-kaur-16-en-18β-oic acid.

9-Methyl-5(10)-octalin-1,6-dione (5)1 has been extensively employed as a starting material for terpenoid and steroid synthesis.2 Its preparation involves high pressure reduction of resorcinol (1) in alkaline solution followed by methylation to give 2-methylcyclohexane-1,3-dione.3 Annelation with methyl vinyl ketone completes the preparation.4 Following published procedures3,4 a competent experimentalist can prepare dione 5 in 35–40% overall yield. In view of the widespread and continued use of this valuable synthetic intermediate we would like to report a modified synthetic scheme whereby dione 5 can be obtained by a two step sequence in greater than 60% overall yield.

The esterifying alcohols of protochlorophyll a and 4-vinyl-(4-desethyl)-protochlorophyll a (purified as the respective pheophytins) from pumpkin seeds were examined by gas chromatography-mass spectrometry. The results of the analysis suggested that pumpkin seed protochlorophyll a is esterified with all possible C20 isoprenoid alcohols between and including geranylgeraniol and phytol, phytol comprising 90% or more of the mixture of esterifying alcohols, and that the 4-vinyl-(4-desethyl)-protochlorophyll a is esterified with farnesol and all possible C20 isoprenoid alcohols between and including geranylgeranoid and phytanol, phytol comprising 50% or more of the mixture of esterifying alcohols. The 4-vinyl-(4-desethyl)-protochlorophyll a from a sample of older mature pumpkin seeds was found to be richer in esterifying alcohols corresponding to isoprenoid precursors of phytol then was the 4-vinyl-(4-desethyl)-protochlorophyll a from a sample of younger mature seeds. Other isoprenoid alcohols may have been present in very minor quantities in the mixtures of esterifying alcohols from the pumpkin seed protochlorophylls but were not looked for in this study. These results are discussed in terms of a biosynthetic accumulation of 4-vinyl-(4-desethyl)-protochlorophyll a in pumpkin inner seed-coat tissue.

The 4,4-bisnorgrayanotoxin skeleton was synthesized from the formylated cross-conjugated cyclohexadienones (5 and 5′) by a photochemical rearrangement. The nonformylated cyclohexadienone (2) gave the spiro compound (7) and the phenols (8 and 9) on photolysis in aqueous acetic acid.

(S)-2-Hydroxycuparene and 3,4′-ethylenebisphenol have been isolated from Marchantia polymorpha Linn., together with a mixture of campesterol, stigmasterol, and β-sitosterol, and other terpenoid constituents. Syntheses of (R)-2-hydroxycuparene and of the bisphenol are reported.

Using combined gas chromatography-mass spectrometry, some 55 constituents of Iridomyrmex humilis have been characterized on the basis of total extraction data, and of data reported for the separate extraction of heads, thoraxes and gasters of this ant. Twenty-seven hydrocarbons—normal, unsaturated, and branched—have been identified. Of these the alkenes (5), (11), (17), and (22) are located primarily, if not wholly, in the heads. Four pyrazines (1), (3), (12), and (21) are present in the heads. The terpenoid, iridomyrmecin (4) is the known major extractive of I. humilis; dolichodial (2) and four related cyclopentanoid monoterpene acids (103), (104), (105), and (106) are now reported from the gasters. The iridoids (2) and (4) are constituents of the anal gland. Three esters—isopropyl myristate, methyl palmitate, and dibutyl phthalate—have been characterized from the total extract. Of these the dibutyl phthalate, mainly found in the thoraxes and gasters, is possibly an artifact. Twelve fatty acids, normal, unsaturated, and branched, and two chlorinated phenols, have also been identified from each extract. The chlorinated phenols are possibly artifacts.

The isolation, absolute stereochemistry, and synthesis of a new C11-terpenoid, 3S,4S,7R-3,7-dimethyl-4,7-oxido-non-8-en-2-one, related to davanone, are described.

U-14C-L-Leucine and 4,5-3H-L-leucine were incorporated into linalool (I) in Cinnamomum Camphora Sieb. var. linalooliferum Fujita in 0.004% yield at the highest value. Its labeling patterns have indicated that DMAPP may originate not only from mevalonic acid but also from leucine not via the acid.

The photosensitized oxygenation of the β,γ-unsaturated ketonic sesquiterpene, davanone, is described. Treatment of davanone epoxide with an acid ion exchange resin yields a stereoisomeric mixture of the davana ethers, sesquiterpenoids containing two reduced furan rings.

Three juvenile hormone analogs (JHA), an acyclic terpene (ACT) [ethyl-3,7,11-trimethyldodeca-2,4-dienoate], a non-terpenoid compound (NT) [acetaldehyde-2-(2-ethoxyethoxy)-ethyl-4-(methylthio)-m-tolyl acetal], and an aromatic terpenoid ether (ATE) [1-(4-ethylphenoxy)-6,7-epoxy-3,7-dimethyl-2-octene] were studied to determine their effect on the embryonic development ofHyalomma (H.) dromedarii. ACT completely blocked embryonic development of eggs that had not yet reached the vitellogenesis stage or were in this stage at the time of ACT application to the female. Development of eggs between vitellogenesis and ovulation stages was partially blocked. Embryogenesis was more or less blocked by NT and ATE, except in a few egg batches from females that had received high NT doses. F1 larval mortality after JHA application to parent females was 100% with ACT, 5 to 100% with NT, and 5 to 85% with ATE.

1 The reactivation of C55-isoprenoid-alcohol phosphokinase apoprotein by a variety of lipids has been investigated. 2 A considerable lack of specificity for the chemical structure of the activating lipid is demonstrated. 3 Reactivation appears to occur by some physical mechanism. An electrostatic interaction of protein and lipid does not appear to be important. 4 All active lipids found are able to swell and become hydrated in aqueous buffer. Some of these lipids were active only after sonication or in the presence of detergent. 5 The hydrated lipid phase is concluded to activate by solubilization, as a liquid-crystalline or micellar solvent for the extremely hydrophobic enzyme apoprotein and for the non-hydrating C55-isoprenoid alcohol.

The inhibition of greening of illuminated etiolated maize seedlings by isonicotinyl hydrazide can be alleviated by serine or pyruvate. The similar inhibition in barley can be reversed only by pyruvate. In both plants earlier intermediates in the glycollate pathway and other related compounds were ineffective in overcoming the inhibition of greening produced by isonicotinyl hydrazide. In maize seedlings radioactivity from l -serine-[3-14C] is poorly incorporated into β-carotene, a typical chloroplast terpenoid, unless glycine and formate or, more effectively, glycine together with isonicotinyl hydrazide are supplied. These supplementations may minimize interconversion of serine and glycine, and hence dilution of radioactivity at C-3 of l -serine by unlabelled C-1 units, before incorporation into terpenoids. The results support the view that in young greening tissue the C2-3 fragment of l -serine can give rise to acetyl-CoA, an obligatory precursor of chloroplast terpenoids.

Two new terpenoid coumarins — mogoltadone and mogoltadin — have been isolated from the roots ofFerula mogoltavica. Mogoltadone has the composition C24H28O4, [α] D 21 -41.7° (c 1.1; chloroform). On the basis of spectral characteristics, it has been shown that it is the ether of umbelliferone and 3-oxo-4,4,10-trimethyl-8-vinyldecalin-9-ylmethanol with the trans linkage of rings A and B and the equatorial orientation of the substituent at C9. Mogoltadin has the composition C24H30O4, [α] D 21 -55° (c 1.0; ethanol) and is the ether of umbelliferone and 3-hydroxy-4,4,10-trimethyl-8-vinyldecalin-9-ylmethanol with the trans linkage of rings A and B and the diequatorial arrangement of the substituents at C3 and C9.

Recently, we isolated dehydroipomeamarone, a new sesquiterpenoid from sweet potato (Ipomoea batatas Lam.) root tissue infected with Ceratocystis fimbriata (Ell. et Halst.). The purpose of this investigation was to determine whether dehydroipomeamarone was a precursor in the biosynthetic pathway of ipomeamarone. The incorporation of acetate-2-(14)C into ipomeamarone was markedly inhibited by the presence of dehydroipomeamarone. Radioactive dehydroipomeamarone was efficiently converted into ipomeamarone, and the compound was biosynthesized earlier than ipomeamarone according to a time course analysis of the production of the terpenoid. These results support the notion that dehydroipomeamarone is an immediate precursor of ipomeamarone. On the other hand, the production of ipomeamarone was slightly lessened in the presence of dehydroipomeamarone. Thus, the marked reduction of acetate-2-(14)C incorporation into ipomeamarone by dehydroipomeamarone may result from both isotopic dilution and an inhibitory effect by exogenous dehydroipomeamarone.

Males of Ips spp. produced the pheromones ipsdienol (2-methyl-6-methylene-2,7-octadien-4-ol) and/or ipsenol (2-methyl-6-methylene-7-octen-4-ol) when exposed to vapours of myrcene, a monoterpene present in their hosts (Pinus spp.). Ips grandicollis and Ips calligraphus require feeding before metabolizing the myrcene, whereas Ips avulsus and Ips paraconfusus produce some pheromone without prior feeding. Topical treatment with ipsdienol results in ipsenol production in both fed and unfed I. paraconfusus males but only in fed I. gradicollis males. I. calligraphus males, which do not produce ipsenol in nature, did not produce any with the topical treatment regardless of prior conditioning. It is concluded that myrcene can serve as a precursor for these terpene alcohols and suggested that ipsenol is produced by the reduction of ipsdienol. Furthermore, the biosynthesis of these pheromones appears to be under some form of control in certain species, with the stimulus for production occurring upon feeding.

CONTENTS INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542 GLYCOSIDE PHYTOTOXINS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544 HeJminthosporoside. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544 Oligosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545 Glycopeptides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 546 Lipomucopolysaccharides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547 Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548 TERPENOID PHYTOTOXINS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548

1. 1. The effects of a new class of inhibitors of cyclic-AMP and cyclic-GMP phosphodiesterases were studied. Three analogs of α-tocopherol, all of them lacking the terpenoid side chain, proved to be potent non-competitive inhibitors of partially purified cyclic-AMP and cyclic-GMP phosphodiesterases from beef liver. All of them were relatively specific for cyclic-AMP phosphodiesterase. The effect on cyclic-GMP phosphodiesterase was much less pronounced. Theophyllin, a methylxanthin, affected both of the enzymes at similar rates. 2. 2. The effect of α-tocopherol deprivation on the concentration of cyclic AMP and two functions controlled by the intracellular concentration of cyclic AMP were investigated. The animals deprived of α-tocopherol had a lower content of glycogen and a higher activity of serine dehydratase in the livers than the control group. The concentration of cyclic AMP in the livers of the rats was not significantly different in both of the groups. 3. 3. The data are discussed with respect to the hypothesis that the long-term effects of α-tocopherol deprivation are related to changes in the regulation of the metabolism of cyclic AMP, caused by alteration of the activity of cyclic-AMP phosphodiesterase.

A bioassay was developed for comparisons of activity of insect growth regulators on Solenopsis invicta Buren. The percentage of pupae developing adult pigmentation was a reliable criterion for IGR activity not previously reported for the imported fire ant and was more readily observed than other morphogenic effects which occurred. The most effective IGR was an aryl terpenoid ether with a 7-alkoxy group for the 6, 7-epoxymoiety. Several other broad spectrum IGR’s showed good activity.

Actinidine, iridodial, citronellal, and iso-valeraldehyde have been identified as major components of the defensive secretions of various staphylinid species. Smaller quantities of hydrocarbons (tridecane and pentadecane) and probably geranial were also detected. The terpenoids are presumably derived from different stages in the same biosynthetic pathway.