19 the Prevalence of Natural 3-Alk(En)Yl-Substituted

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THE PREVALENCE OF NATURAL 3-ALK(EN)YL-SUBSTITUTED PHENOLS AND THEIR POTENTIAL SEMISYNTHESES FROM CASHEW NUT SHELL LIQUID

Stephen JM Mdachi Chemistry Department, University of Dar es Salaam, P.O. Box 35061, Dar es Salaam, Tanzania. E-mail: [email protected] ABSTRACT The focus of this mini-review is to assemble an instructive sample of natural products possessing structural features present in phenolic constituents of Cashew Nut Shell Liquid (CNSL) and, thus, inspire researchers to undertake semisyntheses of these natural products using the relatively abundant phenolic components of CNSL as raw materials. In this review, the author attempts to identify (or point out to) a 3-alk(en)yl-substituted phenolic sub-structure embedded in a particular natural product and reveal the CNSL phenolic component that has the corresponding structural motif. In addition, the author prompts the reader into a thinking process that should eventually lead him/her to developing a comprehensive retrosynthesis of a particular natural product culminating to that CNSL phenolic component as the starting material. Thus, in some way this paper is a tutorial review to the newcomers in the field of natural product synthesis utilizing natural resources. The seasoned synthetic chemists will also benefit from this collection as they guide and inspire their research trainees to take up natural product synthesis. In this article, a brief introduction to the composition and applications of CNSL is presented. This is followed by a compilation from the literature of reported natural products possessing the 3-alk(en)yl-substituted phenolic moiety. Alongside this compilation, a diagnostic discussion is presented aiming at pinpointing CNSL phenols as prospective precursors for the semisyntheses of some selected natural products as illustrative examples.

Key words: Semisynthesis, CNSL phenols, 3-alk(en)yl-substituted phenolic sub-structure, natural products synthesis, natural resources

INTRODUCTION (Figure 1, 9-12), and traces of methylcardol Cashew Nut Shell Liquid/Oil (CNSL) is a (Figure 1, 13-16). Natural CNSL can also be by-product of the cashew processing obtained by physical pressing of the shells industry; its chemical composition has been (extrusion method). Technical CNSL, described as far back as 1967 (Akinhanmi obtained by roasting the shells, contains and Atasie 2008). Based on the method of mostly cardanol (60-65%), cardol (15-20%), extraction from cashew nut shells, CNSL is polymeric material (10%), and traces of classified into two types, solvent-extracted methylcardol. Due to the high temperatures (Natural) CNSL and Technical CNSL. attained (ca. 200 °C) during the roasting Usually, Natural CNSL contains cardol (15- process, anacardic acid decarboxylates to 20%) (Figure 1, 1-4), anacardic acid (60- form cardanol (Kumar et al. 2002). 65%) (Figure 1, 5-8), cardanol (10%)

19 Mdachi, S.J.M. The prevalence of natural 3-alk(en)yl-substituted …..

Figure 1. Structure of Cashew Nut Shell Liquid (CNSL) Constituents

The resourcefulness of CNSL and its isolated constituent phenols from CNSL, individual phenolic constituents cannot be especially cardanol and anacardic acid, have overemphasized. CNSL versatility is evident been extensively utilized in the syntheses of from its diverse uses as a mixture but also numerous polymeric materials (Jinhuo and the numerous applications of its individual Binghuan 1998, Lubi and Thachil 2000, constituent phenols. For example, CNSL by Mkayula et al. 2004, Makame et al. 2005, itself finds applications as an insecticide, Khaokhum et al. 2005, Gopalakrishnan and fungicide, larvicide, anti-termite, corrosion Sujatha 2010, Philip et al. 2012, inhibitor, as well as an additive in many Gopalakrishnan et al. 2012, Mwangi and plastic formulations (Lubi and Thachil 2000, Mbugua 2013). Asogwa et al. 2007, Buchweishaija 2009, Olotuah and Ofuya 2010, Mukhopadhyay et Besides their being sources of polymeric al. 2010, Mann and Kaufman 2012). CNSL products, the CNSL phenols form basic also find applications in industry as a raw precursors for organic synthesis. For material for brake lining, as a water proofing example, over the last one and a half agent, a preservative and in the decades cardanol has been used in the manufacturing of paints and plastics synthesis of products such as quaternary (Akinhanmi and Atasie 2008). Moreover, ammonium salts, hybrid materials, novel CNSL is widely reported for its medicinal fulleropyrrolidines and porphyrins (de properties such as anti-bacterial, anti- Avellar et al. 2000, Attanasi et al. 2009, oxidant, enzyme inhibition and other Mele et al. 2009, and Vasapollo et al. 2011). bioactivities (Himejima and Kubo 1991, Similarly, anacardic acid has also been Muroi et al. 2004, Kubo et al. 2006, utilized in the synthesis of numerous Tsujimoto et al. 2007, Pereira et al. 2008, products including anacardic aldoximes, Stasiuk et al. 2008, de Jesus et al. 2011, novel benzylamines and quinolines, as well Parasa et al. 2011). On the other hand, as urea and thiourea derivatives that have

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biological activities (Tyman and Iddenten approach(es) toward a given 3-alk(en)yl- 2005, Reddy et al. 2011, Vempati et al. substituted phenolic natural product from a 2011, Vempati et al. 2012). Cardol is also CNSL phenol. It must be emphasized that reported as a raw material in the synthesis of the categorization of any naturally occurring lasiodiplodin, a natural product isolated 3-alk(en)yl-substituted phenol into one of from the culture broth of the fungus the three groups (i.e., anacardic acid-, Botrydiplodia theobromae, and a cardanol- and cardol-related) is based on the phosphorylated cardol compound with judgment and convenience of the author. It antioxidant activity (dos Santos and de is certainly possible for a particular Magalhães 1999, Maia et al. 2013). compound to possess structural features belonging to more than one group and that The preceding brief introduction about the such a compound can therefore be classified composition and reported applications of into more than one class. CNSL is certainly not exhaustive. Nevertheless, it provides a panoramic view Anacardic Acid Related Natural Products of the importance of this cheap and The literature abounds in naturally occurring renewable resource. In the section that 3-alk(en)yl-substituted phenolic compounds follows, which is the focus of this review, with structures similar to anacardic acids 5-8 the author compiles from the literature shown in Figure 1 above. Before presenting reported natural products possessing the 3- examples it is important to take note of a alk(en)yl-substituted phenolic pattern. Along nomenclatural clarification of compounds with this compilation, analytical arguments related to 5-8. Since the carboxyl group in pointing to CNSL phenolic constituents as these compounds is given priority over the prospective synthetic precursors for some phenolic hydroxyl group, the anacardic acids selected natural products are given so as are systematically named as 6-alk(en)yl- encourage sustained utilization of CNSL in substituted salicylic acids. We shall natural product synthesis. endeavor to consistently refer to these compounds as 3-alk(en)yl-substituted PREVALENCE AND PROJECTED phenols. However, when the designation 6- SYNTHESES OF NATURAL 3- alk(en)yl-substituted salicylic acid (or ALK(EN)YL-SUBSTITUTED PHENOLS simply 6-alk(en)ylsalicylic acid) is used it FROM CNSL must be taken to refer to the same class of This section presents a wide array of compounds. reported natural products other than (i.e., distinct from) the sixteen (16) CNSL Among the multitude of the anacardic acid constituents depicted in Figure 1. The related natural products, the aromatic presentation is divided into three sections antibiotic 6-methylsalicylic acid (17, Table namely: anacardic acid-, cardanol- and 1) is the simplest. This compound was cardol-related natural products. This is done isolated, along with six other natural so as to facilitate discussions on the products, from Aspergillus flavipes (Nagia et structural similarity between natural al. 2012). Other examples of naturally products being analyzed and the CNSL occurring higher homologues of 6- phenols. This arrangement makes it easier to methylsalicylic acid are shown in Table 1. provide suggestions on possible synthetic

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Table 1: Examples of Anacardic Acid Related Natural Products and Their Source Structure (Side Chain Length and Unsaturation) Source and Reference Aspergillus flavipes (Nagia et al. 2012)

17 (C1) Metapleural gland of ants (Vander Meer 2012)

18 (C3:0) Fungal species (Alternaria sp.) associated with a sea cucumber (Xia et al. 2011) 19 (C3:0) Metapleural gland of ants (Vander Meer 2012)

20 (C5:0) Metapleural gland of ants (Vander Meer 2012)

21 (C7:0) Streptomyces strain (MS53), closely related to Streptomyces laceyi 22 (C11:0) (Lee et al. 2006) Streptomyces strain (MS53), closely related to Streptomyces laceyi 23 (C12:0) (Lee et al. 2006) Ginkgo biloba (He et al. 2000, Wang et al. 2009, Stasiuk and Kozubek 2010, 24 (C13:0) Pszczolkowski et al. 2011) Knema elegans, K. furfuraceae and K. tunuinervia (Pinto and Kijjoa 1990) 25 (C12 + Ph) Ginkgo biloba (He et al. 2000, Wang et al. 2009, Stasiuk and Kozubek 2010, 26 (C17:1) Pszczolkowski et al. 2011) Amphipterygium adstringens (Rivero-Cruz 2011) 27 (C19:1)

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The structural similarity between hydroxybenzoic acid (31), which should act compounds 17-27 (Table 1) and the as the basic raw material for the anacardic acids 5-8 (Fig. 1) is very obvious. semisyntheses of compounds 18-21 via, It is, therefore, quite possible to among others, a Grignard reaction or a synthetically derivatize the relatively Wittig reaction as a key step. The Grignard abundant anacardic acids (5-8) to or Wittig reagent used should have an compounds 17-27. For compounds with the appropriate carbon chain such that when side chain shorter than C8 (for example, 17- combined with the aldehydic carbon of 21), one might saturate the olefinic bonds of compound 31 gives the required chain the side chain of anacardic acid and length in compounds 18-21. Reductive thereafter carry out either benzylic oxidation manipulation of the aldehydic group of or halogenation so as to set the stage for the compound 31 should eventually result into eventual formation of a benzylic double the formation of 17. The NBS route to a bond as shown in compound 30 (Scheme 1). compound similar to 30 is reported in Cleavage of the benzylic double bond in literature (Logrado et al. 2005). compound 30 furnishes 2-formyl-6-

Scheme 1: Proposed synthesis of 31, a raw material for the syntheses of compounds 17-21.

For compounds with the side chain longer butylmagnesium bromide would lead to than C8 (for example, 22-27), it may be assemble the side chains of compounds 22 helpful to exploit the olefinic double bond at and 23, respectively. The proposed synthetic position 8 by cleaving it to obtain a C8 approach summarized in Scheme 2 carbon chain with aldehyde functionality as represents a general idea and, therefore, in a shown in compound 32 (Scheme 2). The comprehensive synthetic planning some aforementioned ozonolytic cleavage has details and refinements may become already been reported (Logrado et al. 2005). necessary. These may include, for example, Once this is accomplished, the required protection of the hydroxyl groups of both the chain length in compounds 22-27 may then phenolic and carboxyl functional groups as be constructed through the reaction of well as change of method in the construction aldehyde 32 obtained with, for example, a of the side chain from compound 32. In the Grignard reagent having an appropriate latter case, one might decide to employ the number of carbon atoms. For example, an Wittig instead of the Grignard method isopropylmagnesium bromide and sec- suggested in Scheme 2.

23 Mdachi, S.J.M. The prevalence of natural 3-alk(en)yl-substituted …..

Scheme 2: Proposed synthesis of 32, a raw material for the syntheses of compounds 22-27.

In some cases the presence of a 3-alk(en)yl- 33-35 and similar compounds through substituted phenolic sub-structure imbedded synthetic manipulations of anacardic acids in a particular natural product may be less 5-8. The 1,2,3-substitution pattern in the obvious than it is in the examples discussed phenolic compounds 33-35 is indicated by so far. For instance, it may be difficult to the box on the left hand side of each point out the similarity between anacardic structure. It must be noted that the 1,2,3- acids 5-8 (Fig. 1) and some naturally numbering in compounds 33-35 does not occurring phenolic compounds such as the represent the standard way used for 8-hydroxy-3,4-dihydroisocoumarin (or 8- nomenclatural purposes of these compounds. hydroxy-3,4-dihydro-1H-2-benzopyran-1- In here the numbering indicates the relative one) 33 and the two anthraquinones 34 and positions of the three substituents on the left 35 depicted in Figure 2. Careful inspection hand side aromatic ring. The intention of of these natural products, however, reveals this numbering is to make easy the that a 3-alk(en)yl-substituted phenolic comparison of the sub-structures in the pattern, similar to that of anacardic acids 5- boxes to the substitution pattern in the 8, forms part of their structures. This implies anacardic acids 5-8. that it may be possible to obtain compounds

Figure 2. Isocoumarins and Anthraquinones with Structural Similarities to Anacardic Acids

Before discussing some potential products with structures analogous to 33 semisynthetic manipulations of anacardic have been reported in the literature and are acids towards compounds similar to 33, it known to be widely distributed in fungi and would be prudent to point out that natural other organisms. In fact natural products that

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have various substituents on different ubiquitous naturally occurring compounds. positions of 33 are commonly known as Selected examples of melleins and melleins. On the other hand, anthraquinones anthraquinones are shown in Table 2. analogous to 34 and 35 make up a class of

Table 2: Examples of Melleins and Anthraquinones Structurally Related to Anacardic Acid. Structure Source and Reference 33 (See Figure 2) Metapleural gland of ants (Vander Meer 2012) 34 (See Figure 2) Micromonospora lupini (Actinomycete) Igarashi et al. 2007 35 (See Figure 2) Same source as compound 34 Metapleural gland of ants (Vander Meer 2012) Stem bark of Oroxylum indicum (L.) 36 Benth. ex Kurz (Maungjunburee 2010) Culture filtrates of Botrosphaeria obtusa (Djoukeng et al. 2009) Culture filtrates of Neofusicoccum parvum (Evidente et al. 2010)

37 Culture filtrates of Neofusicoccum parvum (Evidente et al. 2010)

38 39: R = CHO Roots of Rhus javanica L. var. roxburghiana (Lee et al. 2005)

40: R = CH2OH

Botrosphaeria obtusa (Venkatasubbaiah et al. 1991)

41 42: R1 = H; R2 = OH Culture filtrates of Botrosphaeria obtusa (Djoukeng et al. 2009) 43: R1 = OH; R2 = OH

1 2 44: R = CO2Me; R = OH Xylaria sp. PSU-G12 (an endophytic 1 2 45: R = CO2Me; R = H fungi) (Rukachaisirikul et al. 2013) 46: R1 = Me; R2 = H 1 2 47: R = CO2H; R = H

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Medicinal Chinese herb – Rumex japonicus (Guo et al. 2011)

48 Isolated from Aloe saponaria (Nogueira and Lopes 2011, Huo et al. 2009)

49 Isolated from Streptomyces coelicolor A3 (2) (Bystrykh et al. 1997)

50 51: R1 = H; R2 = H Isolated from Cassia species (Dave 1 2 52: R = H; R = CH2OH and Ledwani 2012) 1 2 53: R = CH3 ; R = CHO 1 2 54: R = H; R = CO2H 1 2 55: R = Gluc; R = CO2H Isolated from Cassia species (Dave and Ledwani 2012)

Retrosynthetic analysis of a mellein such as and refinements, this general synthetic 33 (Fig. 1) could lead to aldehyde 31 design can possibly be extended to the (Scheme 1) as a key intermediate. Scheme 3 semisyntheses of other compounds related to represents possible semisynthetic 33. manipulations of 31 towards the targeted mellein 33.With appropriate modifications

Scheme 3: Proposed synthesis of mellein 33 from the anacardic acid derived aldehyde 31.

The coupling reaction between phthalic anthraquinone nucleus. With this idea in anhydride and its derivatives with other mind, one could possibly transform the benzene derivatives is the most common anacardic acid derived aldehyde 31 to the method used to synthetically assemble an phthalic anhydride 57 (Scheme 4) and,

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thereafter, carry out a Friedel-Crafts in Scheme 4. The conversion of 57 to 51 has acylation of a benzene derivative with 57 to been reported by Dhananjeyan and co- obtain an anthraquinone. For example, a workers (2005) although compound 57 was projected synthesis of anthraquinone 51 obtained from a different source. (Table 2) employing this idea is summarized

Scheme 4: Proposed synthesis of anthraquinone 51 from the anacardic acid derivative 31 (adapted from Dhananjeyan et al. 2005).

Cardanol Related Natural Products from Anacardium occidentale, cardanols are From the chemotaxonomic point of view, also found in Ginkgo biloba, Pistacia vera naturally occurring phenols that are and mycobacterial glycolipids (Tyman 2005, structurally related to the cardanols (i.e., Saitta 2009). Table 3 lists some naturally compounds 9-12, Fig. 1) occur in fewer occurring 3-alk(en)ylphenols and their species compared to the anacardic acids and sources. cardols, which are widely distributed. Apart

Table 3: Examples of 3-Alk(en)ylphenols Structurally Related to Cardanols 9-12. Structure Source and Reference Metapleural gland of ants (Vander Meer 2012); Urine of cattle and buffaloes (Mmongoyo et al. 2012) Metapleural gland of ants (Vander Meer 2012)

Metapleural gland of ants (Vander Meer 2012)

From a Sumatran plant (Takaishi et al. 2004)

Detected in Melanorrhoe austate lacquer (Niimura and Miyakoshi 2003)

27 Mdachi, S.J.M. The prevalence of natural 3-alk(en)yl-substituted …..

Same source as 62;also isolated from Knema furfuraceae (Pinto and Kijjoa 1990)

Isolated from Knema elegans (Pinto and Kijjoa 1990)

Detected from kernels of Pistacia vera L. (Saitta et al. 2009)

From Ginkgo biloba (Wang et al. 2009, Stasiuk and Kozubek 2010)

Same source as 65

Same source as 66

The semisyntheses of the natural products similar patterns as previously discussed for listed in Table 3 can be achieved employing intermediates 31 and 32. an approach that may require the derivatization of the CNSL cardanols 9-12 3-Hydroxybenzadehyde (73) is (Fig. 1) to aldehyde 73 and 74 (Fig. 3) in a commercially available and can also be manner analogous to the way aldehydes 31 synthesized from 3-nitrobenzalhehyde (Scheme 1) and 32 (Scheme 2) were (Woodward 1945). On the other hand, obtained. Further transformations of the key Graham and Tyman (2002) obtained 8-(3- aldehyde intermediates 73 and 74 towards hydroxyphenyl)octanal (74) from compounds 58-72 is expected to follow ozonization of the CNSL cardanols (9-12)

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Figure 3. Aldehydes 73 and 74, key intermediates for the syntheses of compounds 58-72.

Cardol Related Natural Products of more than 100 naturally occurring Phenolic compounds structurally related to resorcinolic lipids has been compiled by the CNSL cardols 1-4 (Fig. 1) are commonly Kozubek and Tyman (1999). The structures called 5-alkylresorcinols (or resorcinolic of a few known natural resorcinolic lipids lipids). These natural products occur widely are given in Table 4, which also provides the in plants, bacteria and in insect sources source of the resorcinolic lipids and (Tyman 2005). 5-Alkylresorcinols are also references to earlier and recent studies. found in mushrooms and other fungi. A list

Table 4: Examples of 5-Alkylresorcinols Structurally Related to Cardols 1-4

Structure Source and Reference Metapleural gland of ants (Vander Meer 2012)

Same source as 75

Isolated from the West Australian shrub Hakea trifurcata (Füstner and Seidel 1997) Isolated from an argentine medicinal plant Lithraea melleoides (López et al. 2005)

29 Mdachi, S.J.M. The prevalence of natural 3-alk(en)yl-substituted …..

Same source as 79

Isolated from the small tree Grevillea whiteana McGillivray (Wang et al. 2009)

Same source as 84

86: R = C17:0 (Saturated) Isolated from the 87: R = C17:1 (Δ8Z) mushroom Merulius 88: R = C17:2 (Δ8Z,11Z ) incarnates (Jin and

89: R = C17:3 (Δ8Z,11Z,16 ) Zjawiony 2006, Saleem et al. 2010) 90: R = C17:3 (Δ9E,11Z,16 )

In addition to 5-alk(en)ylbenzene-1,3-diols either in position 2 or 4 or both positions of shown in Table 4, there are other cardol the benzene ring. A few examples of such related natural products with substituents compounds are depicted in Table 5.

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Table 5: Other Cardol Related Natural Products with Substituents in Position(s) 2 and/or 4. Structure Source and Reference Metapleural gland of ants (Vander Meer 2012)

Same source as 91

Isolated from Knema elegans and K. tunuinervia ssp. setosa (Pinto and Kijjoa 1990)

95: R = Me Isolated from the fungus Aspergillus terreus (Choudhary et al. 2004)

Same source as 95 & 96

Isolated from the fungus Gilmaniella humicola (Wanjiku 2009)

To accomplish the semisyntheses of the patterns as the ones discussed earlier for compounds listed in Tables 4 and 5, one can intermediates 31 and 32. In addition to this possibly make use of an approach that general synthetic strategy, detailed synthetic require the derivatization of the CNSL planning should include synthetic steps that cardols 1-4 (Fig. 1) to aldehyde 99 and 100 address specific structural features of the (Fig. 4) in a manner corresponding to the target natural product. For example, way aldehydes 31 (Scheme 1) and 32 awareness of the presence of extra (Scheme 2) were obtained. Further synthetic substituents in positions 2 and/or 4 in manipulations of the key aldehyde compounds 91-98 (Table 5) should be intermediates 99 and 100 to compounds 75- reflected in the detailed synthetic plans for 98 are expected to follow analogous general these compounds.

31 Mdachi, S.J.M. The prevalence of natural 3-alk(en)yl-substituted …..

Figure 4. Aldehydes 99 and 100, key intermediates for the syntheses of compounds 75-98.

The organic intermediate 3,5- in the field of natural product synthesis dihydroxybenzaldehyde (99) is utilizing natural resources. The experienced commercially available whereas Graham synthetic chemist will also benefit from this and Tyman (2002) obtained 8-(3,5- compilation as a tool for guiding and hydroxyphenyl)octanal (100) from motivating research trainees to take up ozonization of the CNSL cardols (1-4, Fig. natural product synthesis. 1). ACKNOWLEDGEMENTS CONCLUSION I would like to thank my colleague Dr. Based on structural resemblances with the Philip JYN of Chemistry Department, major components of CNSL phenols, a University of Dar es Salaam for his positive categorized compilation of other naturally and cheering remarks during the preparation occurring 3-alk(en)yl-substituted phenolic of this paper. compounds has been given in this mini- review. The selected summaries (Tables 1-5) REFERENCES undoubtedly indicate the extensive Akinhanmi TF and Atasie VN 2008 distribution and diversity of these Chemical Composition and compounds in plants, fungi, bacteria, insects, Physicochemical Properties of etc. Admittedly though, this review has not Cashew Nut (Anacardium furnished an exhaustive compilation of all occidentale) Oil and Cashew Nut the available literature information in this Shell Liquid. Journal of Agricultural, field. This compilation, however, furnishes a Food and Environmental Sciences 2: useful source of and a lead to finding 1-10. interesting natural products as synthetic Asogwa EU, Mokwunye IU, Yahaya LE and targets. The briefly discussed potential Ajao AA 2007 Evaluation of Cashew semisynthetic strategies suggested in this Nut Shell Liquid (CNSL) as a review may serve as a source of inspiration Potential Natural Insecticide Against for undertaking the semisyntheses of these Termites (Soldiers and Workers natural products utilizing the relatively Castes). Res. J. Applied Sci. 2: 939- abundant CNSL phenols. In this article, the 942. potential of CNSL phenols in the Attanasi OA, Mele G, Filippone P, preparation of synthetically useful fine Mazzetto, SE and Vasapollo G 2009 chemicals (such as the 3-substituted phenols Synthesis and Characterization of 31, 32, 73, 74, 99 and 100) has been Novel Cardanol-based highlighted. It is significant to note that 3- Fulleropyrrolidines. ARKIVOC viii: substituted phenols are difficult to prepare 69-84. and, as a consequence, the commercially Buchweishaija J 2009 Phytochemicals as available products are generally expensive. Green Corrosion Inhibitors in Various In general, the author is of the view that this Corrosive Media: A review. Tanz. J. tutorial review will introduce the newcomers Sci. 35: 77-92.

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