Sesquiterpenes as Phytoalexins and Allelopathic Agents - American

Chapter 7

Sesquiterpenes as Phytoalexins and Allelopathic Agents Stella D. Elakovich

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Department of Chemistry, University of Southern Mississippi, Hattiesburg, MS 39406-5043

The plant origin and structure are given for those sesquiterpenes which have been shown to be active as phytoalexins or allelopathic agents. Potato (Solanum tuberosum), pepper (Capsicum annum), tobacco (Nicotiana species), eggplant (Solanum melongena), tomato (Lycopersicon esculentum) and jimsonweed (Datura stramonium), all members of the Solanaceae, are rich sources of sesquiterpenoid phytoalexins. Over twenty furanosesquiterpenoid phyto alexins have been isolated from sweet potato (Ipomoea batatus). Both elm (Ulmus glabra) and cotton (Gossypium species) have also been sources of sesquiterpenoid phytoalexins. Allelopathic sequiterpenoids have been implicated in a limited number of investigations. Potential sesquiterpenoid allelochemicals have been found in Artemisia absenthium, Ambrosia psilostachya, Cyperus serotinus and Lippia nodiflora. Sesquiterpenes frequently occur i n the steam v o l a t i l e e s s e n t i a l o i l s of higher plants. They occur less frequently i n lower plants and i n the animal kingdom although a number of marine organisms have proved to be abundant sources of a novel group of both halogenated and nonhalogenated sesquiterpenes (Réf. 1). A large class of highly oxygenated sesquiterpene lactones has been i s o l a t e d , many from the Compositae, and shown to be bioactive. Stevens (Ref. 2) has recently reviewed these compounds. Plant derived sesquiterpenes include hydrocarbons as w e l l as alcohols, ketones, aldehydes and carboxylic acids. Robinson (Ref. 3) suggests the term "sesquiterpenoid to better describe both hydrocarbon and oxygenated compounds while "sesquiterpene" refers only to hydrocarbons. Many sesquiterpenoids possessing i n t e r e s t i n g b i o l o g i c a l properties have been detected. This chapter w i l l discuss those which have been shown to be active as phytoalexins or a l l e l o p a t h i c agents. The structures of these compounds are given i n Figures 1-8 i n the text. 11

0097-6156/87/0325-0093$06.00/0 © 1987 American Chemical Society

In Ecology and Metabolism of Plant Lipids; Fuller, G., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1987.

ECOLOGY AND METABOLISM OF PLANT LIPIDS

94

ΙΟ

10-epilubimin

1 1

15-dihydrolubimin

R = $CHO

12.

15-dihydro-10-epilubimin R = 3CH OH

8

phytuberol

R =H

R = ocC^OH


2

1A

2-epilubimin

1 5

15-dihydro-2-epilubimin R = CH OH

R = CHO

16

rishitinone

17

oxyglutinosone

2

1 8

epioxylubimin

1 9

acetyldehydrorishitinol

Figure 1. Sesquiterpenoid Stress Metabolites from Potato.



ELAKOVICH Sesquiterpenes

2 Ο

capsidiol

2 1

capsenone

22

glutinosone

Figure 2. Sesquiterpenoid Stress Metabolites from Sweet Pepper (20 and 21) and Tobacco (20) and (22).

23

2 A

2 5

aubergenone

26 9-hydroxynerolidol

9-oxonerolidol

2 7 ll-hydroxy-9,10-dehydronerolidol

Figure 3. Sesquiterpenoid Stress Metabolites from Eggplant.




farnesol

3 2

2 9

ipomeamaronol

2 8

6-oxydendrolasin

ipomeamarone

Figure 4. Biosynthetic Relationship o f Furanosesquiterpenoid Stress Metabolites from Sweet Potato.

3 A

R = CHO

3 7

R = CHO β-costal

7-hydroxycostal Figure 5. Selinene-type Sesquiterpenoid Stress Metabolites from Sweet Potato.




CHO

OH

OH

ÇHO

CHO

OH

HO^ HO

J

A 7 CHO

CH

3

hemigossypol

OH

HO

A 8

6-methoxyhemigossypol

4 9

R = H 6-deoxyhemigossypol

5 Ο

R = OH

51

R = OCH

isohemigossypol 3

gossyvetin

Figure 7. Gossypol Sesquiterpenoid Stress Metabolites from Cotton.




00

7. ELAKOVICH Sesquiterpenes

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Biosynthesis Sesquiterpenoids arise v i a the mevalonate-isopentyl pyrophosphatefarnesyl pyrophosphate pathway with 2-cis-6-trans- or 2-trans-6trans-farnesyl pyrophosphate as the b i o l o g i c a l precursor for almost a l l sesquiterpenoids. Because biosynthetic i n v e s t i g a t i o n s of plants have been hampered by low and nonspecific uptake of added precursors, compartmentation e f f e c t s , rapid turnover of metabolites, and seasonal metabolic v a r i a t i o n s , the majority of biosynthetic i n v e s t i g a t i o n s of sesquiterpenoid biosynthesis have been carried out with fungi (Ref. 4). The recent routine a v a i l a b i l i t y of C nuclear magnetic resonance (nmr) has g r e a t l y s i m p l i f i e d the a b i l i t y to d i r e c t l y locate s i t e s of labeling without recourse to laborious dégradâtive schemes (Ref. 5). This has led to a dramatic increase i n the number of reports on sesquiterpenoid biosynthesis. A number of investigations of phytoalexin biosynthesis have reported added precursor being incorporated at l e v e l s comparable to those seen i n fungal cultures (Ref. 4). Thus phytoalexins may provide a r i c h source of plant sesquiterpenoid biosynthetic information. A recent report by B r i n d l e , eit a l . (Ref. 6) established that p o t a t o - c e l l suspension cultures synthesize and accumulate sesquiterpenoid phytoalexins. This a b i l i t y to e l i c i t terpenoid phytoalexin formation i n c e l l suspension culture should speed the e x p l o i t a t i o n of tissue culture techniques i n the studies of terpenoid phytoalexin biosynthesis. Phytoalexins Phytoalexins are substances that are absent i n normal plant t i s s u e , but are biosynthesized i n response to a challenge. O r i g i n a l l y , phytoalexins were antifungal compounds e l i c i t e d upon i n f e c t i o n of the host plant by some fungi. I t i s now c l e a r that phytoalexins are produced i n plants i n response to other l i v i n g organisms such as b a c t e r i a , viruses and nematodes, and also i n response to treatment with chemicals, mechanical wounding, dehydration, cold or u l t r a - v i o l e t l i g h t . Stoessl et a l . (Ref. 8) suggest that the term p h y t o a l e x i n be applied to any antifungal compound synthesized by the plant i n greatly increased amounts a f t e r fungal i n f e c t i o n , and that the term 'stress metabolite be applied to compounds produced i n response to other challenges. However, other authors use the terms almost interchangably. The amounts of phytoalexins produced from viruses can be as large as 10 to 500 μ g/g tissue. Thus v i r u s infected tissues have been useful for the i s o l a t i o n of new phytoalexins and also the provision of q u a n t i t i e s s u f f i c i e n t f o r studies on t h e i r metabolism and t o x i c i t y (Ref. 7). A 1982 monograph edited by B a i l e y and Mansfield (Ref. 9) provides a thorough review of a l l the various aspects of phytoalexins. 1

1

Phytoalexins from the Solanaceae Most phytoalexin research has been conducted with plants i n the Leguminosae and Solanaceae. Sesquiterpenoid phytoalexins are common i n the Solanaceae, but are not apparent i n the Leguminosae. Kuc (Ref. 10) has recently reviewed phytoalexins from the Solanaceae. In 1976 Stoessl et a l . (Ref. 8) reviewed


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sesquiterpenoid stress compounds of the Solanaceae, and i n 1981 Stothers reviewed these compounds with emphasis on the biosynthetic pathways leading to t h e i r formation (Ref. 11). Potato - Solanum tuberosum. C l a s s i c a l work by Millier and BBrger (Ref. 12) i n 1940 with potatoes began phytoalexin research i n the Solanaceae. They were attempting to produce potato c u l t i v a r s with resistance to Phytophthora infestans, the fungus which causes l a t e b l i g h t disease i n potatoes. They demonstrated that potato tubers infected with P^_ infestans produced low molecular weight f u n g i t o x i c compounds and that the accumulation of these compounds was related to the resistance of the tuber to the fungus. In spite of the great economic importance of c u l t i v a t e d potatoes, i t was some 28 years before a group of Japanese workers (Ref. 13) isolated r i s h i t i n (1) as the f i r s t well-defined phytoalexin from potatoes. Reports of the two a d d i t i o n a l phytoalexins, lubimin (2) (Ref. 14) and phytuberin (3) (Ref. 15), followed quickly. The o r i g i n a l l y reported structure f o r lubimin was l a t e r corrected by Katsui et^ a l . (Ref. 16) and S t o e s s l ejt a l . (Ref. 17) to t h a t shown i n (2). Subsequently r i s h i t i n o l (4) (Ref. 18), 3-hydroxylubimin (5) (Ref. 16a), anhydro-8-rotunol (6) (Ref. 19), solavetivone (7) (Ref. 19) and p h y t u b e r o l (8) (Ref. 20) were i s o l a t e d as sesquiterpenoid stress metabolites (SSMs) of the potato. A l l of these sesquiterpenoids c l e a r l y belong to the same biogenetic group, but the r o l e of each i n disease resistance has not been thoroughly investigated. R i s h i t i n , lubimin, solavetivone and phytuberin are termed phytoalexins. R i s h i t i n , lubimin and solavetivone generally comprise 85% or more of the t o t a l potato derived SSMs with r i s h i t i n often the major SSM (Ref. 10). In d i f f e r e n t experiments using the same potato c u l t i v a r and race of P^_ i n f e s t a n s , Kuc (Ref. 10) has observed e i t h e r r i s h i t i n , lubimin or solavetivone as the major SSM. He suggested that s l i g h t changes i n the p h y s i o l o g i c a l state of the potato tubers and the environment can profoundly influence which of the sesquiterpenoids predominates. None of the compounds ever appears to be induced alone, but not a l l of them are produced i n detectable amounts i n any given s i t u a t i o n . Accumulation of small amounts of the a d d i t i o n a l sesquiterpenoids i s o l u b i m i n (9) (Ref. 21), 10-epilubimin (10), 15dihydrolubimin (11), 15-dihydro-10-epilubimin (12) (Ref. 22), cyclodehydroisolubimin (13) (Ref. 23), 2-epilubimin (14) (Ref. 24), 15-dihydro-2-epilubimin (15) (Ref. 25), r i s h i t i n o n e (16) (Ref. 26), oxyglutinosone (17), epioxylubimin (18) (Ref. 27), and a c e t y l d e h y d r o r i s h i t i n o l (19) (Ref. 28) may be due to synthesis by the host or degradation by host or pathogen of host-synthesized terpenoids, or even to synthesis by a pathogen. (Ref. 10) The r o l e of these compounds as phytoalexins has not been f u l l y investigated. Pepper - Capsicum annuum. The sesquiterpenoid phytoalexin c a p s i d i o l (20) i s formed i n pepper f r u i t a f t e r inoculation with many fungi and at least one bacterium (Ref. 22). I t s skeleton i s i n t e r e s t i n g because the v i c i n a l methyl groups are trans, i n contrast to a l l other previously described eremophilanes (Ref. 11). A second sesquiterpenoid, capsenone, i s also present i n peppers infected with c e r t a i n fungi, but has been shown to be a fungal oxidation product of c a p s i d i o l (Ref. 29). C a p s i d i o l accounts f o r




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about h a l f of the t o t a l ether extractives from the aqueous diffusâtes of peppers inoculated with the fungus M o n i l i n i a f r u c t i c o l a (Ref. 30). The diffusâtes from pepper are thus much less complex than those obtained from potato, or indeed, from any other members of the Solanaceae. Capsidiol may be obtained i n concentrations of up to 0.75 mM i n diffusâtes (Ref. 29). F r u i t s of Capsicum frutescens possess a s t e r i l e c a v i t y into which large quantities of p o t e n t i a l precursors can be a s e p t i c a l l y injected together with fungal spore suspensions with l i t t l e or no mechanical damage. They are thus almost i d e a l f o r host-parasite studies. Ward eit a l . (Ref. 31) compared the f u n g i t o x i c i t y of c a p s i d i o l with that of r i s h i t i n , the major phytoalexin from potatoes, capsenone, and 20 other c a p s i d i o l - r e l a t e d or c a p s i d i o l derived compounds. They used both pathogenic and non-pathogenic fungi. Capsidiol was the most active compound tested, but no c o r r e l a t i o n s were found among the s e n s i t i v i t y to c a p s i d i o l or r i s h i t i n and pathogenicity f o r peppers or potatoes, nor could c o r r e l a t i o n s between structure and a c t i v i t y be drawn. Tobacco - Nicotiana species. Guedes et_ a l . (Ref. 32) reported the accumulation of s i x sesquiterpenoid stress metabolites i n f o l i a g e of Nicotiana tabacum innoculated with Pseudomonas lachrymans, a nonpathogen of tobacco. The infected tobacco foliage accumulated c a p s i d i o l (20), also reported i n infected pepper, as w e l l as r i s h i t i n (1), lubimin (2), phytuberin (3), phytuberol (8) and a trace of what was thought to be solavetivone (7), a l l of which are also found i n infected potato. Maximum accumulation of these SSMs occurred 12-24 hours a f t e r i n f e c t i o n whereas studies of pepper and potato showed maximum accumulation of SSMs a f t e r 48 to 96 hrs. Accumulation of the sesquiterpenoids coincided with the appearance of necrosis, was detected i n and immediately around necrotic t i s s u e , and was not detected i n apparently healthy t i s s u e 5 mm or more from the edges of lesions. Burden ert a l . (Ref. 33) found the sesquiterpenoid glutinosone (22) i n leaves of Nicotiana glutinosa which had been infected with tobacco mosaic v i r u s . Although some i n v e s t i g a t o r s would approve the term 'phytoalexin for a v i r u s induced compound, glutinosone has not yet been reported i n fungal infected tissue of N. glutinosa. Glutinosone could not be detected i n healthy, uninoculated leaves. Both c a p s i d i o l and solavetivone could also be induced by v i r u s i n f e c t i o n . Capsidiol accumulated i n both N. tabacum and N. Cleveland!i infected with tobacco necrosis v i r u s , (Ref. 34) and solavetivone accumulated i n N^ tabaccum infected with tobacco mosaic v i r u s (Ref. 35). 1

Eggplant - Solanum melongena. F r u i t s of eggplants produce sesquiterpenoid phytoalexins, thus conforming to the pattern of other members of the Solanaceae (Ref. 36). Eggplants (Solanum melongena 'Black Beauty ) r o u t i n e l y accumulated phytoalexins when innoculated with spore suspensions of M o n i l i n i a f r u c t i c o l a as w e l l as with four other fungi. The ethyl ether extract of the d i f f u s a t e obtained was very complex and required repeated chromatography f o r the separation of pure components. Seven compounds were i s o l a t e d , accounting for about 30% of the extract. Of these seven, lubimin (2), which i s also a potato phytoalexin, and a compound having 1




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structure (23) were the two most active compounds i n spore germination i n h i b i t i o n assays, but with the exception of aubergenone (24), a l l compounds had appreciable a c t i v i t y against P. infestans (Ref. 36). Compound (23) and another of the compounds i s o l a t e d were almost c e r t a i n l y a r t i f a c t s since they were not detected i n fresh crude extracts. The remaining three i d e n t i f i e d compounds had structures (25), (26), and (27). A l l f i v e of the fungi tested induced a l l of the compounds, although i n d i f f e r i n g amounts, which suggests that phytoalexin production i s nonspecific. The structure of aubergenone was revised to that of (24) by Murai and coworkers (Ref. 37). The revised structure, 11-hydroxy4a,5a-eudesm-l-en-3-one (24) i s the only stress compound with a 5a-eudesmane skeleton among the Solanaceae metabolites and hence stands on unique biogenetic grounds (Ref. 37). Tomato - Lycopersicon esculentum. The tomato has not been investigated as thoroughly as potatoes, and the only sesquiterpenoid stress compound so f a r i d e n t i f i e d i s r i s h i t i n (1), the main potato phytoalexin (Ref. 38). The tomato derived extracts from which r i s h i t i n can be i s o l a t e d are complex. I t i s l i k e l y that other sesquiterpenoids w i l l be i s o l a t e d from these complex mixtures i n time (Ref. 8). Jimsonweed - Datura stramonium. Like other Solanaceae, Datura stramonium produces antifungal sesquiterpenoid compounds i n response to i n o c u l a t i o n with M o n i l i n i a f r u c t i c o l a and several other fungi (Ref. 39). Three of the four phytoalexins thus f a r i d e n t i f i e d are also accumulated by other Solanaceous species. Lubimin (2) i s also produced both i n potato and eggplant, c a p s i d i o l (20) i s the main phytoalexin i n sweet pepper f r u i t , and hydroxylubimin (5) i s also found i n potato. The fourth compound 2,3-dihydroxygermacrene, i s unique to Datura and could serve as an almost d i r e c t precursor of lubimin and 4-hydroxylubimin as w e l l as other Solanaceae phytoalexins (Ref. 39a). Phytoalexins from Other Families Convolvulaceae - Sweet Potato (Ipomoea batatus). In the forty years since Hiura (Ref. 40) f i r s t i s o l a t e d ipomeamarone (28) from sweet potatoes, the furanosesquiterpenoid stress metabolites of t h i s plant have been extensively investigated and over twenty furano-sesquiterpenoids have been i s o l a t e d (Ref. 41, 42). Extensive biosynthetic i n v e s t i g a t i o n s have provided the f o l l o w i n g r e l a t i o n s h i p s among these phytoalexins (Ref. 43). 6-0xodendrolasin (29) which i s accumulated upon either i n f e c t i o n by Ceratocystis f i m b r i a t a or HgC^ treatment, i s the close precursor of dehydroipomeamarone (30) which appears to be the immediate biosynthetic precursor of ipomeamarone (28) and also the precursor of ipomeabisfuran (31), which, l i k e (29) i s accumulated upon e i t h e r C f i m b r i a t a i n f e c t i o n or HgC^ treatment. Ipomeamarone (28) i s the precursor of ipomeamaronol (32). A l l f i v e of these compounds (28) - (32) have the properties of phytoalexins. They are produced i n r e l a t i v e l y large amounts i n response to i n f e c t i o n and they show antifungal a c t i v i t y . Schneider et^ a l . (Ref. 42) recently characterized nine new minor stress metabolites from C. f i m b r i a t a



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infected tissue and have proposed a d e t a i l e d biogenic scheme which includes 19 furanoterpenoids and furanoterpenoid-related stress metabolites. At about the same time, Schneider and Nakanishi (Ref. 44) reported the presence of two new compounds of the eudesmane skeleton, 7-hydroxycostol (33) and 7-hydroxycostal (34), as w e l l as three known selinene derivatives, compound (35), 3-costol (36) and 3-costal (37). These f i v e compounds are included i n the biogenic scheme of Schneider et^ a l . (Ref. 42). The eudesmane skeleton i s b i o g e n i c a l l y d i f f e r e n t from that of furanosesquiterpenoids, and thus the sweet potato represents a unique case of a plant which concurrently produces two s k e l e t a l l y d i f f e r e n t series of sesquiterpenoid phytoalexins (Ref. 44). Ulmaceae - Elm (Ulmus glabra). Eight cadinane-type sesquiterpenes were i s o l a t e d from Wych elm (Ulmus glabra) branches which had been infected with the fungi Ceratocystis ulmi (Causative agent of Dutch Elm disease), Coriolus v e r s i c o l o r (a white rot fungus) and Chondrostereum purpureum (causal agent of s i l v e r leaf disease i n many trees) (Ref. 45). None of the eight compounds (38) - (45) were observed i n chromatograms of sapwood of healthy branches, although a l l compounds (38) - (43) had been previously reported as heartwood constituents i n various elm species. The mansonones Ε (42) and F (43) had previously been i s o l a t e d from hollandica f o l l o w i n g i n f e c t i o n by C^ ulmi. The role of these tree phytoalexins i n disease resistance has yet to be determined, but the present evidence suggests that they provide l i t t l e e f f e c t i v e fungal resistance (Ref. 45). Malvaceae - Cotton (Gossypium species). Gossypol (46), a dimeric sesquiterpene of the cadalane class, i s a natural pigment found i n tissues of healthy cotton plants, but, because of c e r t a i n properties i t i s often classed as a phytoalexin. I t s biosynthesis was reviewed i n 1979 by Heinstein et^ a l . (Ref. 46). Gossypol accumulation can be induced by inoculation of cotton tissues with V e r t i c i l l i u m albo-atrum (causative agent of w i l t disease) or Rhizopus nigricans, or by chemical treatment with cupric or mecuric ions (Ref. 47). P u r i f i e d gossypol proved active against fungi as measured by fungal spore germination assays, and s i m i l a r amounts of gossypol were accumulated from those cotton c u l t i v a r s having gossypol and those which have l i t t l e or no free gossypol. Thus, gossypol may be classed as a phytoalexin. B e l l et a l . (Ref. 48) confirmed that hemigossypol (47) i s the major phytoalexin formed i n both G^ barbadense and G^_ hirsutum upon V e r t i c i l l i u m i n f e c t i o n . Hemigossypol, 6-methoxy-hemigossypol (48) and 6-deoxyhemigossypol (49) were the major sesquiterpenoid stress metabolites from the infected tissue of a range of Gossypium species (Ref. 48). Russian workers have i s o l a t e d isohemigossypol (50) and gossyvertin (51) from stem tissue of cotton plants infected with V^_ dahliae (Ref. 47). Very l i t t l e gossypol was found i n t h i s same tissue. I t thus appears that gossypol i t s e l f i s not the most important contributor to the phytoalexin response of cotton even though i t has antifungal properties.


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A l l e l o p a t h i c Agents In h i s c l a s s i c a l paper t i t l e d "The Influence of One Plant on Another-Allelopathy", Molisch i n 1937 coined the term 'allelopathy to r e f e r to biochemical interactions between a l l types of plants including microorganisms. He included both i n h i b i t o r y and stimulatory interactions (Ref. 49). Rice, (Ref. 50) i n the f i r s t e d i t i o n of h i s comprehensive monograph, A l l e l o p a t h y , used the term to include only i n h i b i t o r y interactions. In the recent second e d i t i o n of h i s monograph, Rice reverts to Molisch's use of the term because the published l i t e r a t u r e convinced him that most, or perhaps a l l , organic compounds that are i n h i b i t o r y at some concentrations may be stimulatory at some much lesser concentrations (Ref. 51). Most secondary metabolites can be c l a s s i f i e d into f i v e major categories: phenylpropanes, acetogenins, terpenoids, steroids, and a l k a l o i d s (Ref. 51). Higher plants produce a great variety of terpenoids, but only a very few sesquiterpenoids have been implicated i n a l l e l o p a t h y (Ref. 51). Artemisia absinthium produces three sesquiterpene i n h i b i t o r s , β-carophyllene (52), bisabolene (53) and another component which forms chamazulene i n the open a i r (Ref. 52). Both Ambrosia psilostachya and A^ acanthicarpa produce several sesquiterpene lactones, but none of them have been confirmed as a l l e l o c h e m i c a l s (Ref. 51). V o l a t i l e plant growth i n h i b i t o r s i s o l a t e d from western ragweed (Ambrosia psilostachya) may be sesquiterpenes. Komai e^t a l . (Ref. 53) found gc-ms evidence of the sesquiterpenes 3-selinene (54), methyl farnesate, farnesyl acetate (55), and farnesol (56) present i n an i n h i b i t o r y f r a c t i o n i s o l a t e d from water nutgrass (Cyperus serotinus ). This f r a c t i o n at 300 ppm i n h i b i t e d lettuce germination and also i n h i b i t e d growth of lettuce and r i c e seedlings as w e l l as nutgrass i t s e l f . The authors conclude that the sesquiterpenes are responsible f o r the observed allelopathic effects. We (Ref. 54) have recently i d e n t i f i e d the sesquiterpenes 3-caryophyllene (52), 6-cadimene (57), a-bergamotene (58), 3-bisabolene (53), a-copaene (59), calamenene (60) and 4,10dimethyl-7-isopropylbicyclo[4.4.0]-1,4-decadiene from the steam v o l a t i l e s of the creeping perennial herb L i p p i a n o d i f l o r a ( f a m i l y Verbenaceae) which i s known f o r i t s rampant growth. Extracts of L. n o d i f l o r a reduced l e t t u c e seedling r a d i c a l length as compared to controls suggesting the presence of a l l e l o c h e m i c a l s . β-Caryophyllene comprises almost 20% of the i d e n t i f i e d hydrocarbons. The steam v o l a t i l e s of L. n o d i f l o r a also contain the monoterpenes É^pinene and £-cymene which Asplund (Ref.55) found i n h i b i t o r y toward radish seed germination. These terpenes may w e l l be acting as a l l e l o c h e m i c a l s i n n o d i f l o r a , contributing to i t s a b i l i t y to grow rampantly and to i n h i b i t lettuce seedling growth.


1

Literature Cited 1.

P. J. Scheuer, Ed., Marine Natural Products, Vol. 1, Academic Press, New York, 1978, pp. 125 and 177.




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2. Κ. L. Stevens, "Biological Activity and Chemistry of Sesquiterpene Lactones", in W. D. Ness, G. Fuller, and L.-S. Tsai, eds., Isopentenoids in Plants: Biochemistry and Function, Marcel Dekker, Inc., New York, NY, 1984, pp. 65-80. 3. T. Robinson, The Organic Constituents of Higher Plants, 4th Ed., Cordus Press, North Amherst, Mass, 1980, p. 134. 4. D. E. Cane, "Biosynthesis of Sesquiterpenes", in J. W. Porter and S. L. Spurgeion, eds., Biosynthesis of Isoprenoid Compounds, Vol. I, John Wiley and Sons, NY, 1981, pp. 284-374. 5. J. R. Hanson, "The Biosynthesis of Some Sesquiterpenoids", Pure Appl. Chem., 53, 1155-1162 (1981). 6. P. A. Brindle, P. J. Kuhn and D. R. Threlfall, "Accumulation of Phytoalexins in Potato-cell Suspension Cultures", Phytochemistry, 22, 2719-2721 (1983). 7. J. A. Bailey and R. A. Skipp, "Toxicity of Phytoalexins", Ann. Appl. Biol., 89, 354-358 (1978). 8. A. Stoessl, J. B. Stothers and E. W. B. Ward, "Sesquiterpenoid Stress Compounds of the Solanaceae", Phytochemistry, 15, 855872 (1976). 9. J. A. Bailey and J. W. Mansfield, eds., Phytoalexins, John Wiley and Sons, New York, 1982. 10. J. Kuć, "Phytoalexins from the Solanaceae", in J. A. Bailey and J. W. Mansfield, eds., Phytoalexins, John Wiley and Sons, New York, 1982, pp. 81-105. 11. J. B. Stothers, "Sesquiterpenes - Biosynthetic Studies with C and H Magnetic Resonance - A Synthetic Approach via Homoenolization", Pure Appl. Chem., 53., 1241-1258 (1981). 12. K. O. Müller and H. Börger, "Experimentelle Untersuchungen uber die Phytophthora - Resistenz der Kartoffel", Arb. Biol. Anst. Reichsanst. (Berl.), 23, 189-231 (1940). 13. K. Tomiyama, T. Sakuma, N. Ishizaka, N. Sato, N. Katsui, M. Takasugi and T. Masamune, "A New antifungal Substance Isolated from Resistant Potato Tuber Tissue Infected by Pathogens", Phytopathology, 58, 115-116 (1968). 14. O.L.Ozeretskovskaya, Ν. I. Vasyukova, and L. V. Metlitskii, Dokl. Bot. Sci., 187-189, 158 (1969). 15. J. Varns, J. Kućand E. Williams, "TerpenoidAccumulationas a Biochemical Response of the Potato Tuber to Phytophthora infestans", Phytopathology, 61, 174-177 (1971). 16. (a) N. Katsui, A. Matsunaga, and T. Masamune, "The Structure of Lubimin and Oxylubimin, Antifungal Metabolites from Diseased Potato Tubers", Tetrahedron Lett., 4483-4486 (1974). (b) N. Katsui, A. Matsunaga, H. Kitahara, F. Yagihashi, A. Murai, T. Masamune and N. Sato, "Lubimin and Oxylubimin. The Structure Elucidation", Bull. Chem. Soc. Jpn., 50, 1217-1225 (1977). 17. A. Stoessl, J. B. Stothers and E. W. B. Ward, "Lubimin: A Phytoalexin of Several Solanaceae. Structure, Revision and Biogenetic Relationships", J. Chem. Soc. Chem. Comm., 709-710 (1974). 18. N.Katsui,A. Matsunaga, K. Imaizumi, T. Masamune and K. Tomiyama, "The Structure and Synthesis of Rishitinol, A New Sesquiterpene Alcohol from Diseased Potato Tubers", Tetrahedron Lett., 83-86 (1971). 13

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19. D. T. Coxon, K. R. Price, B. Howard, S. F. Osmon, Ε. B. Kalan and R. M. Zacharius, "Two New Vetispirane Derivatives: Stress Metabolites from Potato (Solanum tuberosum) tubers", Tetrahedron Lett. 2921-2924 (1974). 20. (a) K. R. Price, B. Howard and D. T. Coxon, "Stress Metabolite Production in Potato Tubers infected by Phytophthora infestans, Fusarium avenaceum and Phoma exigua", Physiol. Plant Pathol., 9, 189-197. (b) D. T. Coxon, K.R. Price, B. Howard and R. F. Curtis, "Metabolites from Microbially Infected Potato. Part 1, Structure of Phytuberin", Chem. Soc. Perkin, 53-59 (1977). 21. A. Stoessl, J. B. Stothers and E. W. B. Ward, "Sesquiterpenoid Stress Compounds of the Solanaceae", Phytochemistry, 15, 855872 (1976). 22. A. Stoessl, E. W. B. Ward and J. B. Stothers, "Biosynthetic Relationships of Sesquiterpenoidal Stress Compounds from the Solanaceae", in P. A. Hedin, ed., Host Plant Resistance to Pests, Amer. Chem. Soc., Washington, DC, 1977, pp. 61-77. 23. D. T. Coxon, K. R. Price, J. B. Stothers and A. Stoessl, "Cyclodehydroisolubimin: A New Tricyclic Sesquiterpene from Potato Tubers Inoculated with Phytophthora infestans", J. Chem. Soc. Chem. Comm., 348-349 (1979). 24. N.Katsui,F. Yagihashi, A. Matsunaga, K. Orito, A. Murai, and T. Masamune, "The Structure of Epilubimin, A Stress Metabolite from Diseased Potato Tubers", Chem. Lett., 723-724 (1977). 25. A. Stoessl and J. B. Stothers, "2-Epi and 15-dihydro-2epilubimin: New Stress Compounds from the Potato", Can. J. Chem., 58, 2069-2072 (1980). 26. N. Katsui, F. Yagihashi, A. Murai and T. Masamune", Structure of Rishitinone, a Valencane Stress Metabolite in Diseased Potato", Bull. Chem. Soc. Jpn., 55, 2428-2433 (1982). 27. N. Katsui, F. Yagihashi, A. Murai and T. Masamune, "Structure of Oxyglutinosone and Epioxylubimin, Stress Metabolites from Diseased Potato Tubers", Chem. Lett., 1205-1206 (1978). 28. L. M. Alves, R. M. Kirchner, D. T. Lodato, P. B. Nee, J. M. Zappia, M. L. Chichester, J. D. Stuart, Ε. B. Kalan and J. C. Kissinger, "Acetyldehydrorishitinol, A Rishitinol-Related Potato Stress Metabolite", Phytochemistry, 23, 537-538 (1984). 29. E. W. B. Ward and A. Stoessl, "Postinfectional inhibitors from Plants. III. Detoxification of Capsidiol, an Antifungal Compound from Peppers", Phytopathology, 62, 1186-1187 (1972). 30. A. Stoessl, C. H. Unwin, and E. W. B. Ward, "Postinfectional Inhibitors from Plants. I. Capsidiol, and Antifungal Compound from Capsicum frutescens", Phytopathology Z., 74, 141-152 (1972). 31. E. W. B. Ward, C.H. Unwin, and A.Stoessl,"Postinfectional Inhibitors from Plants. XIII. Fungitoxicity of the Phytoalexin, Capsidiol, and Related Sesquiterpenes", Can. J. Bot., 52, 2481-2488 (1974). 32. M. E. M. Guedes, J. Kuć, R. Hammerschmidt and R. Bostock, "Accumulation of Six Sesquiterpenoid Phytoalexins in Tobacco Leaves Infiltrated with Pseudomonas lachrymans", Phytochemistry, 21, 2987-2988 (1982).



7.


107

33. R. S. Burden, J. A. Bailey and G. G. Vincent, "Glutinosone, A New Antifungal Sesquiterpene from Nicotiana glutinosa Infected with Tobacco Mosaic Virus", Phytochemistry, 14, 221-223 (1975). 34. J. A. Bailey, R. S. Burden, and G. G. Vincent, "Capsidiol: An Antifungal Compound Produced in Nicotiana tobacum and N. clevelandii Following Infection with Tobacco Necrosis Virus", Phytochemistry, 14, 597 (1975). 35. R. Uegaki, T. Fujimori, S. Kubo and K. Kato, "Sesquiterpenoid Stress Compounds from Nicotiana Species", Phytochemistry, 20, 1567-1568 (1981). 36. E. W. B. Ward, C. H. Unwin, J. Hill, and A. Stoessl, "Sesquiterpenoid Phytoalexins from Fruits of Eggplants", Phytopathology, 65, 859-863 (1975). 37. (a) A. Murai, A. Abiko, M. Ono, N. Katsui, and T. Masamune, "Structure Revision and Biogenetic Relationship of Aubergenone, a Sesquiterpenoid Phytoalexin of Eggplants", Chem. Lett., 1209-1212 (1978). (b) A. Murai, A. Abiko, M. Ono, and T. Masamune, "Synthesis of Aubergenone, a Sesquiterpenoid Phytoalexin from Diseased Eggplants", Bull. Chem. Soc. Jpn., 55, 1191-1194 (1982). 38. N. Sato, K. Tomiyama and N. Katsui, "Isolation of Rishitin from Tomato Plants", Ann. Phytopathol. Soc. Japan, 34, 344-345 (1968). 39. (a) E. W. B. Ward, C. H. Unwin, G. L. Rock, and A. Stoessl, "Postinfectional Inhibitors from Plants. XXIII. Sesquiterpenoid Phytoalexins from Fruit Capsules of Datura stramonium", Can. J. Bot., 54, 25-29 (1976). (b) G. I. Birnbaum, C. P. Huber, M. L. Post, and J.B. Stothers "Sesquiterpenoid Stress Compounds of Datura stramonium: Biosynthesis of the Three Major Metabolites from [1,2- C] Acetate and the X-ray Structure of 3-Hydroxylubimin", J. Chem. Soc. Chem. Comm., 330-331 (1976). 40. M. Hiura, "Studies in Storage and Rot of Sweet Potato", Rep. Gifu Agric. Coll., 50, 1-5 (1943). 41. L. T. Burka and L. Kuhnert, "Biosynthesis of Furanosesquiterpenoid Stress Metabolites in Sweet Potatoes (Ipomoea batata). Oxidation of Ipomeamarone to 4hydroxymyoporone", Phytochemistry, 16, 2022-2023 (1977). 42. J. A. Schneider, J. Lee, Y. Naya, K. Nakanishi, K. Oba and I. Uritani, "The Fate of the Phytoalexin Ipomeamarone: Furanoterpenes and Butenolides from Ceratocystis fimbriata Infected Sweet Potatoes", Phytochemistry, 23(4), 759-764 (1984). 43. I. Ito, N. Kato, and I. Uritani, "Biochemistry of Two New Sesquiterpenoid Phytoalexins from Sweet Potato Roots", Agric. Biol. Chem., 48(1), 159-164 (1984) and references therein. 44. J. A. Schneider and K. Nakanishi, "A New Class of Sweet Potato Phytoalexins", J. Chem. Soc. Chem. Commun., 353-355 (1983). 45. R. S. Burden and M. S. Kemp, "Sesquiterpene Phytoalexins from Ulmus glabra", Phytochemistry, 23, 383-385 (1984). 46. P. Heinstein, R. Widmaier, P. Wegner, and J. Howe, "Biosynthesis of Gossypol", Recent Adv. Phytochem., 12, 313333 (1979). 13



108


47. D. T. Coxon, "Phytoalexins from Other Families", Chapter 4 in J. A. Bailey and J. W. Mansfield, eds., Phytoalexins, John Wiley and Sons, New York (1982), pp. 116-118. 48. A. A. Bell, R. D. Stipanovic, C. R. Howell and P. A. Fryxell, "Antimicrobial terpenoids of Gossypium: Hemigossypol, 6Methoxyhemigossypol and 6-Deoxyhemigossypol", Phytochemistry, 14, 225-231 (1975). 49. H. Molisch, "Der Einfluss einer Pflanze auf die andere -Allelopathie", Fischer, Jena (1937). 50. E. L. Rice, Allelopathy, Academic Press, New York, 1974. 51. E. L. Rice, Allelopathy, 2nd Ed., Academic Press, New York, 1984. 52. G. Grummer, "The Role of Toxic Substances in the Interrelationships Between Higher Plants", in F. L. Mitthorpe, ed., Mechanisms in Biological Competition, Academic Press, New York (1961), pp. 224-225. 53. K. Komai, Y. Sugiwaka and S. Sato, "Plant-growth Retardant of Extracts Obtained from Water Nutgrass (Cyperus serotinus Rottb.)", Kinki Daigaku Nogakubu Kiyo, 1981, (14), 57-65. Chem. Abstr., 95, 162961c (1981). 54. S. D. Elakovich and K. L. Stevens, "Volatile Constituents of Lippia nodiflora", J. Nat. Prod., 48, 504-506 (1985). 55. R. O. Asplund, "Monoterpenes: Relationship Between Structure and Inhibition of Germination", Phytochemistry, 7, 1995-1997 (1968). Received May 1, 1986


Sesquiterpenes as Phytoalexins and Allelopathic Agents - American

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