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Synthesis of New Agrochemicals

  • Paulo Marcos DonateEmail author
  • Daniel Frederico
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  • 284 Downloads

Abstract

The constantly growing world population calls for effective means of sustainable food production. This chapter will address some general aspects of the chemical action of products that protect crops against pest attack and the implications of these agrochemicals for the environment. The main types of active ingredients used in agrochemicals and their historical development will be concisely approached. The organic synthesis of original molecules and/or the structural modification of natural products that are already being used in agriculture will also be briefly discussed. This discussion will show some useful and versatile tools to obtain modern molecules with advantageous biological activities in agriculture. Given the need for further advances in crop protection, recently developed agrochemicals that can pave the way for future research, such as nanofertilizers, nanopesticides, and nanobiosensors, will be described. Finally, this chapter will discuss current challenges in the synthesis of agrochemicals, as well as cutting-edge developments in the design and synthesis of new agrochemicals, including the invention of more selective and environmentally friendly active ingredients, which will help to face the ongoing challenges of weed and pest resistance.

Keywords

Agrochemical Crop protection Pesticide Organic synthesis Structural modification Regulatory norms 

References

  1. Abad MJ, Ansuategui M, Bermejo P (2007) Active antifungal substances from natural sources. ARKIVOC vii:116–145Google Scholar
  2. Alavanja MCR (2009) Pesticides use and exposure extensive worldwide. Rev Environ Health 24:303–309PubMedPubMedCentralGoogle Scholar
  3. Alavanja MCR, Bonner MR (2012) Occupational pesticide exposures and cancer risk: a review. J Toxicol Environ Health B 15:238–263Google Scholar
  4. Alexandratos N, Bruinsma J (2012) World agriculture towards 2030/2050: the 2012 revision. ESA working paper no. 12-03, Food and Agriculture Organization of the United Nations, Rome, IT. Available at http://www.fao.org/docrep/016/ap106e/ap106e.pdf
  5. Anastas PT, Warner JC (1998) Green chemistry: theory and practice. Oxford University Press, New York, USGoogle Scholar
  6. Anderson AC (2003) The process of structure-based drug design. Chem Biol 10:787–797PubMedGoogle Scholar
  7. Anderson JC, Ley SV (1990) Chemistry of insect antifeedants from Azadirachta indica (part 6): synthesis of an optically pure acetal intermediate for potential use in the synthesis of azadirachtin and novel antifeedants. Tetrahedron Lett 31:431–432Google Scholar
  8. Baker DR, Umetsu NK (eds) (2001) Agrochemical discovery. American Chemical Society, Washington, USGoogle Scholar
  9. Basarab GS, Jordan DB, Gehret TC, Schwartz RS, Wawrzak Z (1999) Design of scytalone dehydratase inhibitors as rice blast fungicides: derivatives of norephedrine. Bioorg Med Chem Lett 9:1613–1618PubMedGoogle Scholar
  10. Basarab GS, Jordan DB, Gehret TC, Schwartz RS (2002) Design of inhibitors of scytalone dehydratase: probing interactions with an asparagine carboxamide. Bioorg Med Chem Lett 10:4143–4154Google Scholar
  11. Batish DR, Setia N, Singh HP, Kohli RK (2004) Phytotoxicity of lemon-scented eucalypt oil and its potential use as a bioherbicide. Crop Prot 23:1209–1214Google Scholar
  12. Batish DR, Singh HP, Setia N, Kohli RK, Kaur S, Yadav SS (2007) Alternative control of littleseed canary grass using eucalypt oil. Agron Sustain Dev 27:171–177Google Scholar
  13. Batish DR, Singh HP, Kohli RK, Kaur S (2008) Eucalyptus essential oil as a natural pesticide. For Ecol Manage 256:2166–2174Google Scholar
  14. Bechinger C, Giebel KF, Schnell M, Leiderer P, Deising HB, Bastmeyer M (1999) Optical measurements of invasive forces exerted by appressoria of a plant pathogenic fungus. Science 285:1896–1899PubMedGoogle Scholar
  15. Begley MJ, Crombie L, Hadi HBA, Josephs JL (1989) Synthesis of novel labile rotenoids with unnatural trans-B/C ring systems. J Chem Soc Perkin Trans I:204–205Google Scholar
  16. Berman HM (2008) The protein data bank: a historical perspective. Acta Crystallogr A 64:88–95PubMedGoogle Scholar
  17. Berman HM, Westbrook J, Feng Z, Gilliland G, Bhat TN, Weissig H, Shindyalov IN, Bourne PE (2000) The protein data bank. Nucleic Acids Res 28:235–242PubMedPubMedCentralGoogle Scholar
  18. Berman HM, Battistuz T, Bhat TN, Bluhm WF, Bourne PE, Burkhardt K, Feng Z, Gilliland G, Iype L, Jain S, Fagan P, Marvin J, Padilla D, Ravichandran V, Schneider B, Thanki N, Weissig H, Westbrook JD, Zardecki C (2002) The protein data bank. Acta Crystallogr D 58:899–907PubMedGoogle Scholar
  19. Bhan S, Mohan L, Srivastava CN (2018) Nanopesticides: a recent ecofriendly approach in insect pest management. J Entomol Res 42:263–270Google Scholar
  20. Bilton JN, Broughton HB, Jones PS, Ley SV, Rzepa HS, Sheppard RN, Slawin AMZ, Williams DJ, Lidert Z, Morgan ED (1987) An X-ray crystallographic, mass spectroscopic, and NMR study of the limonoid insect antifeedant azadirachtin and related derivatives. Tetrahedron 43:2805–2815Google Scholar
  21. Binetti R, Costamagna FM, Marcello I (2008) Exponential growth of new chemicals and evolution of information relevant to risk control. Ann Ist Super Sanità 44:13–15PubMedGoogle Scholar
  22. Bocquet N, Nury H, Baaden M, Le Poupon C, Changeaux JP, Dalarue M, Corringer PJ (2009) X-ray structure of a pentameric ligand-gated ion channel in an apparently open conformation. Nature 457:111–114PubMedGoogle Scholar
  23. Brocksom TJ, Vieira YW, Nakamura J, Finelli FG, Brocksom U (2007) A concise synthesis of the 1,6-disubstituted eudesmane sesquiterpene carbon skeleton. J Braz Chem Soc 18:448–452Google Scholar
  24. Brocksom TJ, Donatoni MC, Uliana M, Vieira Y (2010) A reação de Diels-Alder no início do século vinte um. Quim Nova 33:2211–2218Google Scholar
  25. Butterworth JH, Morgan ED (1968) Isolation of a substance that suppresses feeding in locust. Chem Commun 35:23–24Google Scholar
  26. Carruthers W (1990) Cycloaddition reactions in organic synthesis. In: Tetrahedron organic chemistry series, vol 8. Pergamon Press, Oxford, GBGoogle Scholar
  27. Carvalho FP (2006) Agriculture, pesticides, food security and food safety. Environ Sci Policy 9:685–692Google Scholar
  28. Carvalho FP (2017) Pesticides, environment, and food safety. Food Energy Sec 6:48–60Google Scholar
  29. Casida JE (2009) Pest toxicology: the primary mechanisms of pesticide action. Chem Res Toxicol 22:609–619PubMedGoogle Scholar
  30. Chhipa H (2017) Nanopesticide: current status and future possibilities. Agric Res Technol 5:1–4Google Scholar
  31. Cioc R, Ruijter E, Orru RVA (2014) Multicomponent reactions: advanced tools for sustainable organic synthesis. Green Chem 16:2958–2975Google Scholar
  32. Corey EJ (2002) Catalytic enantioselective Diels-Alder reactions: methods, mechanistic fundamentals, pathways, and applications. Angew Chem Int Ed Engl 41:1650–1667PubMedGoogle Scholar
  33. Corsi C, Lamberth C (2015) New paradigms in crop protection research: registrability and cost of goods. In: Maienfisch P, Stevenson TME (eds) Discovery and synthesis of crop protection products. American Chemical Society, Washington, US, pp 25–37Google Scholar
  34. Crombie L, Freeman PW, Whiting DA (1973) A new synthesis of rotenoids. Application to 9-demethylmunduserone, mundeserone, rotenonic acid, dalpanol, and rotenone. J Chem Soc Perkin Trans I:1277–1285Google Scholar
  35. Dagani R (1999) Presidential green chemistry challenge awards recognize five technologies for their environmental friendliness. Chem Eng News 77:30–32Google Scholar
  36. Dejonghe W, Okamoto M, Cutler SR (2018) Small molecules probes of ABA biosynthesis and signaling. Plant Cell Physiol 59:1490–1499PubMedGoogle Scholar
  37. Dostál J, Bochořáková H, Táborská E, Slavík J (1996) Structure of sanguinarine base. J Nat Prod 59:599–602Google Scholar
  38. Durand-Reville T, Gobbi LB, Gray BL, Ley SV, Scott JS (2002) Highly selective entry to the azadirachtin skeleton via a Claisen rearrangement/radical cyclization sequence. Org Lett 4:3847–3850PubMedGoogle Scholar
  39. Elango G, Rahuman A, Zahir AA, Marimuthu S (2010) Evaluation of repellent properties of botanical extracts against Culex tritaeniorhynchus Giles (Diptera: Culicidae). Parasitol Res 107:577–584PubMedGoogle Scholar
  40. Erlanson DA, McDowell RS, O’Brien T (2004) Fragment-based drug discovery. J Med Chem 47:3463–3482PubMedGoogle Scholar
  41. European Environment Agency (2013) Report no 1/2013. Late lessons from early warnings: science, precaution, innovation. Copenhagen, DKGoogle Scholar
  42. Eurostat (2012) The REACH baseline study, 5 years update summary report. Available at http://ec.europa.eu/eurostat/en/web/products-statistical-working-papers/-/KS-RA-12-024
  43. FAO (2006) Guidelines on efficacy evaluation for the registration of plant protection products. Food and Agricultural Organization of the United Nations. Available at http://www.fao.org/fleadmin/templates/agphome/documents/Pests_Pesticides/Code/Efficacy.pdf
  44. FAO Statistics (2017) Food and Agriculture Organization of the United Nations. Available at http://www.fao.org/faostat/en/#home
  45. FAO Statistical Yearbook (2013) World food and agriculture. Food and Agriculture Organization of the United Nations, Rome, ITGoogle Scholar
  46. Forsyth SA, Gunaratne HQN, Hardacre C, McKeown A, Rooney DW (2006) One-pot multistep synthetic strategies for the production of fenpropimorph using an ionic liquid solvent. Org Process Res Dev 10:94–102Google Scholar
  47. Fraceto LF, Grillo R, Medeiros GA, Scognamiglio V, Rea G, Bartolucci C (2016) Nanotechnology in agriculture: which innovation potential does it have? Front Environ Sci 4:20Google Scholar
  48. Fukui K, Nakayama M, Harano T (1967) A new synthesis of dehydromunduserone. Experientia 23:613–614Google Scholar
  49. Fukuzaki T, Kobayashi S, Hibi T, Ikuma Y, Ishihara J, Kanoh N, Murai A (2002) Studies aimed at the total synthesis of azadirachtin. A modeled connection of C-8 and C-14 in azadirachtin. Org Lett 4:2877–2880PubMedGoogle Scholar
  50. Gilland B (2015) Nitrogen, phosphorus, carbon and population. Sci Progr 98:379–390PubMedGoogle Scholar
  51. Gillij YG, Gleiser M, Zygadlo JA (2008) Mosquito repellent activity of essential oils of aromatic plants growing in Argentina. Bioresour Technol 99:2507–2515PubMedGoogle Scholar
  52. Gnankiné O, Bassolé IHN (2017) Essential oils as an alternative to pyrethroids’ resistance against Anopheles species complex Giles (Diptera: Culicidae). Molecules 22(10):1321PubMedCentralGoogle Scholar
  53. González JOW, Jesser EN, Yeguerman CA, Ferrero AA, Band BF (2017) Polymer nanoparticles containing essential oils: new options for mosquito control. Environ Sci Pollut Res 24:17006–17015Google Scholar
  54. Govorushko S (2018) Human-insect interactions. CRC Press, Boca Raton, USGoogle Scholar
  55. Guan AY, Liu C, Yang X, Dekeyser M (2014) Application of the intermediate derivatization approach in agrochemical discovery. Chem Rev 114:7079–7107PubMedGoogle Scholar
  56. Guan AY, Liu CL, Sun XF, Xie Y, Wang MA (2016) Discovery of pyridine-based agrochemicals by using intermediate derivatization methods. Bioorg Med Chem 24:342–353PubMedGoogle Scholar
  57. Hao GF, Jiang W, Ye YN, Wu FX, Zhu XL, Guo FB, Yang GF (2016) ACFIS: a web server for fragment-based drug discovery. Nucleic Acids Res 44:W550–W556PubMedPubMedCentralGoogle Scholar
  58. Hassankhani A (2015) A rapid, one-pot, multi-component route to 4,4′-(arylmethylene)bis(3-methyl-1-phenyl-1h-pyrazol-5-ols. J Mex Chem Soc 59:1–4Google Scholar
  59. Helander JDM, Vaidya AS, Cutler SR (2016) Chemical manipulation of plant water use. Bioorg Med Chem 24:493–500PubMedGoogle Scholar
  60. Henry KJJ, Fraser-Reid B (1994) Free radical methodology for carbohydrate to carbocycle transformations: an efficient synthesis of the tricyclic dihydrofuran portion of azadirachtin. J Org Chem 59:5128–5129Google Scholar
  61. Hibbs RE, Gouaux E (2011) Principles of activation and permeation in an anion-selective Cys-loop receptor. Nature 474:54–60PubMedPubMedCentralGoogle Scholar
  62. Hörnberg A, Tunemalm AK, Ekström F (2007) Crystal structures of acetylcholinesterase in complex with organophosphorus compounds suggest that the acyl pocket modulates the aging reaction by precluding the formation of the trigonal bipyramidal transition state. Biochemistry 46:4815–4825PubMedGoogle Scholar
  63. Hou QQ, Jing YF, Shao XS (2017) Synthesis and insecticidal activities of 1,8-naphthyridine derivatives. Chin Chem Lett 28:1723–1726Google Scholar
  64. Huang L, Guan T, Qian Y, Huang M, Tang X, Li Y, Sun H (2011) Anti-inflammatory effects of maslinic acid, a natural triterpene, in cultured cortical astrocytes via suppression of nuclear factor-kappa B. Eur J Pharmacol 672:169–174PubMedGoogle Scholar
  65. Huang Y, Liu Y, Liu Y, Song H, Wang Q (2016) C ring may be dispensable for β-carboline: design, synthesis, and bioactivities evaluation of tryptophan analog derivatives based on the biosynthesis of β-carboline alkaloids. Bioorg Med Chem 24:462–473Google Scholar
  66. Huang JL, Min L, Xu H (2017) Semisynthesis of some matrine ether derivatives as insecticidal agents. RSC Adv 7:15997–16004Google Scholar
  67. Huang J, Lv M, Thapa S, Xu H (2018) Synthesis of novel quinolinomatrine derivatives and their insecticidal/acaricidal activities. Bioorg Med Chem Lett 28:1753–1757PubMedGoogle Scholar
  68. Huisgen R (1961) 1,3 dipolar cycloadditions. Proc Chem Soc 357–396Google Scholar
  69. Hummelbrunner LA, Isman MB (2001) Acute, sublethal, antifeedant and synergistic effects of monoterpenoid essential oil compounds on the tobacco cutworm Spodoptera litura (Lep. Noctuidae). J Agric Food Chem 49:715–720PubMedGoogle Scholar
  70. Hurst P, Hay A, Dudley N (1994) The pesticides handbook. Journeyman, London, GBGoogle Scholar
  71. Ishihara J, Fukuzaki T, Murai A (1999a) Synthetic studies on azadirachtin (Part 3): asymmetric synthesis of the tricyclic dihydrofuran moiety of azadirachtin. Tetrahedron Lett 40:1907–1910Google Scholar
  72. Ishihara J, Yamamoto Y, Kanoh N, Murai A (1999b) Synthetic studies on azadirachtin: construction of the highly functionalized decalin moiety of azadirachtin. Tetrahedron Lett 40:4387–4390Google Scholar
  73. Ishihara J, Ikuma Y, Hatakeyama S, Suzuki T, Murai A (2003) Synthesis of the tricyclic dihydrofuran moiety of azadirachtin: efficient transformation of the Claisen rearrangement intermediate into a functionalized tricyclic dihydrofuran core. Tetrahedron 59:10287–10294Google Scholar
  74. Isman MB (2000) Plant essential oils for pest and disease management. Crop Prot 19:603–608Google Scholar
  75. Jeanmart S (ed) (2016) Recent developments in agrochemistry. Bioorg Med Chem 24:315–500Google Scholar
  76. Jeanmart S, Edmunds AJF, Lamberth C, Pouliot M (2016) Synthetic approaches to the new agrochemicals. Bioorg Med Chem 24:317–341PubMedGoogle Scholar
  77. Jeschke P (2012) The unique role of halogen substituents in the design of modern crop protection compounds. In: Jeschke P, Krämer W, Schirmer U, Witschel M (eds) Modern methods in crop protection research. Wiley-VCH, Weinheim, DE, pp 73–128Google Scholar
  78. Jeschke P (2018) Current status of chirality in agrochemicals. Pest Manage Sci 74:2389–2404Google Scholar
  79. Jia ZX, Luo YC, Xu PF (2011) Highly enantioselective synthesis of polysubstituted tetrahydroquinolines via organocatalytic Michael/Aza-Henry tandem reactions. Org Lett 13:832–835PubMedGoogle Scholar
  80. Jordan DB, Lessen TA, Wawrzak Z, Bisaha JJ, Gehret TC, Hansen SL, Schwartz RS, Basarab GS (1999) Design of scytalone dehydratase inhibitors as rice blast fungicides: (N-phenoxypropyl)-carboxamides. Bioorg Med Chem Lett 9:1607–1612PubMedGoogle Scholar
  81. Kah M, Kookana RS, Gogos A, Bucheli TD (2018) A critical evaluation of nanopesticides and nanofertilizers against their conventional analogues. Nat Nanotechnol 13:677–684PubMedGoogle Scholar
  82. Khanna R, Gupta S (2018) Agrochemicals as a potential cause of ground water pollution: a review. Int J Chem Stud 6:985–990Google Scholar
  83. Khater HF (2012) Prospects of botanical biopesticides in insect pest management. Pharmacologia 3:641–656Google Scholar
  84. Kelly WL (2008) Intramolecular cyclizations of polyketide biosynthesis: mining for a “Diels-Alderase”? Org Biomol Chem 6:4483–4493PubMedGoogle Scholar
  85. Klebe G (2000) Recent developments in structure-based drug design. J Mol Med 78:269–281PubMedGoogle Scholar
  86. Koehler PG, Belmont RA (1998) Basic pesticide training manual (SM-59). Ohio State University, Columbus, USGoogle Scholar
  87. Koprna R, De Diego N, Dundálková L, Spíchal L (2016) Use of cytokinins as agrochemicals. Bioorg Med Chem 24:484–492PubMedGoogle Scholar
  88. Kraus W, Bokel M, Bruhn A, Cramer R, Klaiber I, Klenk A, Nagl G, Poehnl H, Sadlo H, Volger B (1987) Structure determination by NMR of azadirachtin and related compounds from Azadirachta indica A. Juss (Meliaceae). Tetrahedron 43:2817–2830Google Scholar
  89. Kumar M, Shamsi T, Parveen R, Fatima S (2017) Application of nanotechnology in enhancement of crop productivity and integrated pest management. In: Prasad R, Kumar M, Kumar V (eds) Nanotechnology: an agricultural paradigm. Springer, Singapore, SG, pp 361–371Google Scholar
  90. Kurihara N, Miyamoto J (eds) (1998) Chirality in agrochemicals. Wiley, Chichester, GBGoogle Scholar
  91. Kusano M, Koshino H, Uzawa J, Fujioka S, Kawano T, Kimura Y (2000) Nematicidal alkaloids and related compounds produced by the fungus Penicillium cf. simplicissimum. Biosci Biotechnol Biochem 64:2559–2568PubMedGoogle Scholar
  92. Lamberth C, Dinges J (2012) The significance of heterocycles for pharmaceuticals and agrochemicals. In: Lamberth C, Dinges J (eds) Bioactive heterocyclic compound classes: agrochemicals. Wiley-VCH, Weinheim, DE, pp 3–20Google Scholar
  93. Lamberth C, Jeanmart S, Luksch T, Plant A (2013) Current challenges and trends in the discovery of agrochemicals. Science 341:742–746PubMedGoogle Scholar
  94. Ley SV (2005) Development of methods suitable for natural product synthesis: the azadirachtin story. Pure Appl Chem 77:1115–1130Google Scholar
  95. Li H, Guan A, Huang G, Liu CL, Li Z, Xie Y, Lan J (2016a) Design, synthesis and structure-activity relationship of novel diphenylamine derivatives. Bioorg Med Chem 24:453–461PubMedGoogle Scholar
  96. Li L, Li Z, Wang K, Liu Y, Li Y, Wang Q (2016b) Synthesis and antiviral, insecticidal, and fungicidal activities of gossypol derivatives containing alkylimine, oxime or hydrazine moiety. Bioorg Med Chem 24:474–483PubMedGoogle Scholar
  97. Lindell SD, Pattenden LC, Shannon J (2009) Combinatorial chemistry in the agrosciences. Bioorg Med Chem 17:4035–4046PubMedGoogle Scholar
  98. Londershausen M (1996) Review: approaches to new parasiticides. Pest Manage Sci 48:269–292Google Scholar
  99. Loso MR, Benko Z, Buysse A, Johnson TC, Nugent BM, Rogers RB, Sparks TC, Wang NX, Watson GB, Zhu Y (2016) SAR studies toward the pyridine moiety of the sap-feeding insecticide sulfoxaflor. Bioorg Med Chem 24:378–382PubMedGoogle Scholar
  100. Lv P, Chen Y, Shi T, Wu X, Qing XL, Hua R (2018) Synthesis and fungicidal activities of sanguinarine derivatives. Pestic Biochem Physiol 147:3–10PubMedGoogle Scholar
  101. McCann SF, Annis GD, Shapiro R, Piotrowski DW, Lahm GP, Long JK, Lee KC, Hughes MM, Myers BJ, Griswold SM, Reeves BM, March RW, Sharpe PL, Lowder P, Barnette WE, Wing KD (2001) The discovery of indoxacarb: oxadiazines as a new class of pyrazoline-type insecticides. Pest Manage Sci 57:153–164Google Scholar
  102. McCann SF, Cordova D, Andaloro JT, Lahm GP (2012) Sodium channel-blocking insecticides: indoxacarb. In: Krämer W, Schirmer U, Jeschker P, Witschel M (eds) Modern crop protection compounds, 2nd edn. Wiley-VCH, Weinheim, DE, pp 1257–1273Google Scholar
  103. McDougall P (2016) The cost of new agrochemical product discovery, development and registration in 1995, 2000, 2005–8 and 2010–2014. R&D expenditure in 2014 and expectations for 2019. Report, Croplife America, Washington, US. Available at https://croplife.org/wp-content/uploads/2016/04/Cost-of-CP-report-FINAL.pdf
  104. Mergott DJ, Frank SA, Roush WR (2004) Total synthesis of (–)-spinosyn A. PNAS 101:11955–11959PubMedGoogle Scholar
  105. Merzendorfer H (2013) Chitin synthesis inhibitors: old molecules and new developments. Insect Sci 20:121–138PubMedGoogle Scholar
  106. Miyano M (1965) Rotenoids. XX. Total synthesis of rotenone. J Am Chem Soc 87:3958–3962PubMedGoogle Scholar
  107. Miyano M, Kobayashi A, Matsui M (1960) Synthese and configurational elucidation of rotenoids. Part XVIII. The total synthesis of the natural rotenone. Bull Agric Chem Soc Jpn 24:540–542Google Scholar
  108. Montilla MP, Agil A, Navarro MC, Jiménez MI, García-Granados A, Parra A, Cabo MM (2003) Antioxidant activity of maslinic acid, a triterpene derivative obtained from Olea europaea. Planta Med 69:472–474PubMedGoogle Scholar
  109. Nakao T, Banba S (2016) Broflanilide: a meta-diamine insecticide with a novel mode of action. Bioorg Med Chem 24:372–377PubMedGoogle Scholar
  110. Nakao T, Banba S, Nomura M, Hirase K (2013) Meta-diamide insecticides acting on distinct sites of RDL GABA receptor from those for conventional noncompetitive antagonists. Insect Biochem Mol Biol 43:366–375PubMedGoogle Scholar
  111. Nejma AB, Znati M, Daich A, Othman M, Lawson AM, Jannet HB (2018) Design and semisynthesis of new herbicide as 1,2,3-triazole derivatives of the natural maslinic acid. Steroids 138:102–107PubMedGoogle Scholar
  112. Nerio LS, Olivero-Verbel J, Stashenko E (2010) Repellent activity of essential oils: a review. Bioresour Technol 101:372–378PubMedGoogle Scholar
  113. Nishikimi Y, Iimori T, Sodeoka M, Shibasaki M (1989) Synthetic studies of azadirachtin. Synthesis of the cyclic acetal intermediate in the naturally occurring form. J Org Chem 54:3354–3359Google Scholar
  114. Nuruzzaman M, Rahman MM, Liu Y, Naidu R (2016) Nanoencapsulation, nano-guard for pesticides: a new window for safe application. J Agric Food Chem 64:1447–1483PubMedGoogle Scholar
  115. Oberlander H, Silhacek DL (1998a) Mode of action of insect growth regulators in Lepidopteran tissue culture. Pest Manage Sci 54:300–302Google Scholar
  116. Oberlander H, Silhacek DL (1998b) New perspectives on the mode of action of benzoylphenyl urea insecticides. In: Ishaaya I, Degheele D (eds) Insecticides with novel modes of action: mechanism and application. Springer, Berlin, DE, pp 92–105Google Scholar
  117. Oerke EC (2006) Crop losses to pests. J Agric Sci 144:31–43Google Scholar
  118. Oh MS, Yang JY, Lee HS (2012) Acaricidal toxicity of 2′-hydroxy-4′-methylacetophenone isolated from Angelicae koreana roots and structure-activity relationships of its derivatives. J Agric Food Chem 60:3606–3611PubMedGoogle Scholar
  119. Oliveira JL, Campos EVR, Fraceto LF (2018) Recent developments and challenges for nanoscale formulation of botanical pesticides for use in sustainable agriculture. J Agric Food Chem 66:8898–8913Google Scholar
  120. Omolo MO, Okinyo D, Ndiege IO, Lwande W, Hassanali A (2004) Repellency of essential oils of some Kenyan plants against Anopheles gambiae. Phytochemistry 65:2797–2802PubMedGoogle Scholar
  121. PAN Pesticide Database (2016) Pesticide Action Network (PAN), North America (Oakland, CA). Available at www.pesticideinfo.org
  122. Pasteris RJ, Hanagan MA, Bisaha JJ, Finkelstein BL, Hoffman LE, Gregory V, Andreassi JL, Sweigard JA, Klyashchitsky BA, Henry YT, Berger RA (2016) Discovery of oxathiapiprolin, a new oomycete fungicide that targets an oxysterol binding protein. Bioorg Med Chem 24:354–361PubMedGoogle Scholar
  123. Pawar VC, Thaker VS (2006) In vitro efficacy of 75 essential oils against Aspergillus niger. Mycoses 49:316–323PubMedGoogle Scholar
  124. Peshin R, Dhawan AK (eds) (2009) Integrated pest management. In: Innovation-development process, vol 1. Springer, Netherlands, NLGoogle Scholar
  125. Plant A (2010) Crop protection chemistry: challenges and opportunities in the 21st century. Agrow Silver Jubilee Issue, XI–XVGoogle Scholar
  126. Prasad R, Kumar V, Prasad KS (2014) Nanotechnology in sustainable agriculture: present concerns and future aspects. Afr J Biotech 13:705–713Google Scholar
  127. Queirós L, Vidal T, Nogueira AJA, Gonçalves FJM, Pereira JL (2018) Mixture toxicity assisting the design of eco-friendlier plant protection products: a case study using a commercial herbicide combining nicosulfuron and terbuthylazine. Sci Rep 8:5547PubMedPubMedCentralGoogle Scholar
  128. Ray DE (1991) Pesticides derived from plants and other organisms. In: Hayes WJ Jr, Laws ER Jr (eds) Handbook of pesticide toxicology. Academic Press, San Diego, US, pp 585–636Google Scholar
  129. Reyes-Zurita FJ, Pachon-Pena G, Lizárraga D, Rufino-Palomares EE, Cascante M, Lupianez JA (2011) The natural triterpene maslinic acid induces apoptosis in HT-29 colon cancer cells by a JNK-p 53-dependent mechanism. BMC Cancer 11:154Google Scholar
  130. Rios MY, Córdova-Albores LC, Ramírez-Cisneros MA, King-Díaz B, Lotina-Hennsen B, Rivera IL, Miranda-Sánchez D (2018) Phytotoxic potential of Zanthoxylum affine and its major compound linarin as a possible natural herbicide. ACS Omega 3:14779–14787PubMedPubMedCentralGoogle Scholar
  131. Rodrigues SM, Demokritou P, Dokoozlian N, Hendren CO, Karn B, Mauter MS, Sadik OA, Safarpour M, Unrine JM, Viers J, Welle P, White JC, Wiesner MR, Lowry GV (2017) Nanotechnology for sustainable food production: promising opportunities and scientific challenges. Environ Sci Nano 4:767–781Google Scholar
  132. Roser ME, Ortiz-Ospina E (2017) World population growth. Published online at OurWorldInData.org. Available at https://ourworldindata.org/world-population-growth/
  133. Sakurai K, Tanino K (2015) Synthetic studies on azadirachtin: construction of the ABC ring system via the Diels-Alder reaction of a vinyl allenylsilane derivative. Tetrahedron Lett 56:496–499Google Scholar
  134. Sasaki I, Yamashita K (1979) Synthesis of (–)-rotenone. Agric Biol Chem 43:137–139Google Scholar
  135. Schleifer KJ (2007) Virtual screening in crop protection research. In: Ohkawa H, Miyagawa H, Lee PW (eds) Pesticide chemistry. Wiley-VCH, Weinheim, DE, pp 77–88Google Scholar
  136. Sharpless KB, Kolb HC, Finn MG (2001) Click chemistry: diverse chemical function from a few good reactions. Angew Chem Int Ed Engl 40:2004–2021PubMedGoogle Scholar
  137. Shi H, Tan C, Zhang W, Zhang Z, Long R, Gong J, Luo T, Yang Z (2016) Gold-catalyzed enantio- and diastereoselective syntheses of left fragments of Azadirachtin/Meliacarpin-type limonoids. J Org Chem 81:751–771PubMedGoogle Scholar
  138. Singh D, Singh DJ (1991) Synthesis and antifungal activity of some 4-arylmethylene derivatives of substituted pyrazolones. J Indian Chem Soc 68:165–167Google Scholar
  139. Singh RN, Saratchandra B (2005) The development of botanical products with special reference to seri-ecosystem. Casp J Environ Sci 3:1–8Google Scholar
  140. Singh HP, Batish DR, Kohli RK (2003) Allelopathic interactions and allelochemicals: new possibilities for sustainable weed management. Crit Rev Plant Sci 22:239–311Google Scholar
  141. Singh Z, Kaur J, Kaur R, Hundal SS (2016) Toxic effects of organochlorine pesticides: a review. Am J Biosci 4:11–18Google Scholar
  142. Solomon KR, Stephenson GR, Corrêa CL, Zambrone FAD (2010) Praguicidas e o meio ambiente. ILSI Brasil, São Paulo, Brazil, pp 109–110Google Scholar
  143. Sparks TC, Lorsbach BA (2017) Perspectives on the agrochemical industry and agrochemical discovery. Pest Manage Sci 73:672–677Google Scholar
  144. Stanescu MD (2014) Pesticides: synthesis, activity and environmental aspects. Available at https://www.researchgate.net/publication/291688542_PESTICIDES_Synthesis_Activity_and_Environmental_Aspects
  145. Stocking EM, Williams RM (2003) Chemistry and biology of biosynthetic Diels-Alder reactions. Angew Chem Int Ed Engl 42:3078–3115PubMedGoogle Scholar
  146. Stoner K (2004) Bulletin #7144, Approaches to the biological control of insects. Available at https://extension.umaine.edu/publications/7144e/
  147. Sun F, Zhu F, Shao X, Li Z (2015) One-pot, three-component synthesis of 1,8-naphthyridine derivatives from heterocyclic ketene aminals, malononitrile dimer, and aryl aldehydes. Synlett 26:2306–2312Google Scholar
  148. Syngenta (2014) Introduction to agrochemicals and modern agronomy. Available at http://www.oxfordsynthesiscdt.ox.ac.uk/resources/SBM-CDT-Agrochemistry.pdf
  149. Talbot NJ (2003) On the trail of a cereal killer: exploring the biology of Magnaporthe grisea. Annu Rev Microbiol 57:177–202PubMedGoogle Scholar
  150. Tambo GMR, Bellus D (1991) Chirality and crop protection. Angew Chem Int Ed Engl 30:1193–1386Google Scholar
  151. Tan C, Chen W, Mu X, Chen Q, Gong J, Luo T, Yang Z (2015) Synthetic progress toward azadirachtins. 2. Enantio- and diastereoselective synthesis of the right-wing fragment of 11-epi-azadirachtin I. Org Lett 17:2338–2341PubMedGoogle Scholar
  152. Taylor MD, Klaine SJ, Carvalho FP, Barcelò D, Everaarts J (eds) (2003) Pesticide residues in coastal tropical ecosystems. Distribution, fate and effects. Taylor & Francis Publ., CRC Press, London, GBGoogle Scholar
  153. Tebourbi O, Sakly M, Rhouma KB (2011) Molecular mechanisms of pesticide toxicity. In: Stoytcheva M (ed) Pesticides in the modern world: pests control and pesticides, exposure and toxicity assessment. InTech Publ. Available at http://www.intechopen.com/books/pesticides-in-the-modernworld-pests-control-and-pesticides-exposure-and-toxicity-assessmentGoogle Scholar
  154. Theodoridis G (2006) Fluorine-containing agrochemicals: an overview of recent development. In: Tressaud A (ed) Fluorine and the environment: agrochemicals, archaeology, green chemistry and water. Elsevier, Amsterdam, NL, pp 121–175Google Scholar
  155. Tice CM (2001) Selecting the right compounds for screening: does Lipinski’s rule of 5 for pharmaceuticals apply to agrochemicals? Pest Manage Sci 57:3–16Google Scholar
  156. Tice CM (2002) Selecting the right compounds for screening: use of surface-area parameters. Pest Manage Sci 58:219–233Google Scholar
  157. Tomizawa M, Casida JE (2005) Neonicotinoid insecticide toxicology: mechanisms of selective action. Annu Rev Pharmacol Toxicol 45:247–268PubMedGoogle Scholar
  158. Touw WG, Baakman C, Black J, te Beek TAH, Krieger E, Joosten RP, Vriend G (2015) A series of PDB—related databanks for everyday needs. Nucleic Acids Res 43:D364–D368PubMedGoogle Scholar
  159. Turner CJ, Tempesta MS, Taylor RB, Zagorski MG, Termini JS, Schroeder DR, Nakanishi K (1987) An NMR spectroscopic study of azadirachtin and its trimethyl ether. Tetrahedron 43:2789–2803Google Scholar
  160. Ujvary I (2010) Pest control agents from natural products. In: Krieger R (ed) Hayes’ handbook of pesticide toxicology, 3rd edn. Academic Press, New York, US, pp 119–229Google Scholar
  161. United Nations (2015) Department of economic and social affairs, population division. World population prospects: the 2015 revision, key findings and advance tables. Working paper no. ESA/P/WP.241, United Nations, New York, US. Available at https://esa.un.org/unpd/wpp/publications/files/key_findings_wpp_2015.pdf
  162. Veitch GE, Beckmann E, Burke BJ, Boyer A, Ayats C, Ley SV (2007) A relay route for the synthesis of azadirachtin. Angew Chem Int Ed Engl 46:7633–7635PubMedGoogle Scholar
  163. Walter MW (2002) Structure-based drug design of agrochemicals. Nat Prod Rep 19:278–291PubMedGoogle Scholar
  164. Walter H (2012) Pyrazole carboxamide fungicides inhibiting succinate dehydrogenase. In: Lamberth C, Dinges J (eds) Bioactive heterocyclic compound classes: agrochemicals. Wiley-VCH, Weinheim, DE, pp 175–193Google Scholar
  165. War AR, Paulraj MG, Ahmad T, Buhroo AA, Hussain B, Ignacimuthu S, Sharma HC (2012) Mechanisms of plant defense against insect herbivores. Plant Signal Behav 7:1306–1320PubMedPubMedCentralGoogle Scholar
  166. Whitford F, Pike D, Burroughs F, Hanger G, Johnson B, Brassard D, Blessing A (2006) The pesticides marketplace. Discovery and developing new products. PPP-71. Pardue University, West Lafayette, US. Available at https://www.extension.purdue.edu/extmedia/PPP/PPP-71.pdf
  167. World Health Organization (2012) The WHO recommended classification of pesticides by hazard and guidelines to classification. Geneva, ITGoogle Scholar
  168. World Health Organization (2017) Agrochemicals, health and environment: directory of resources. Available at http://www.who.int/heli/risks/toxics/chemicalsdirectory/ en/index1.html
  169. Xie Y, Chi HW, Guan AY, Liu CI, Ma HJ, Cui DI (2016) Synthesis and evaluation of substituted 3-(pyridine-2-yl)benzenesulfonamide derivatives as potent herbicidal agents. Bioorg Med Chem 24:428–434PubMedGoogle Scholar
  170. Yang Y, Liu Y, Song H, Li S, Wang Q (2016) Additive effects on the improvement of insecticidal activity: design, synthesis and insecticidal activity of novel pymetrozine derivatives. Bioorg Med Chem 24:391–402PubMedGoogle Scholar
  171. Yang R, Guo Y, Zhang Y, Xu H (2018) Semisynthesis of new ethers from furyl-ring-based acylation derivatives of fraxinellone as insecticidal agents against Mythimna separata Walker in vivo. Chin Chem Lett 6:995–997Google Scholar
  172. Yin J, Wang Y, Gilbertson LM (2018) Opportunities to advance sustainable design of nano-enabled agriculture identified through a literature review. Environ Sci Nano 5:11–26Google Scholar
  173. Yu LPC, Kim YS, Tong L (2010) Mechanisms for the inhibition of the carboxyltransferase domain of acetyl-coenzyme A carboxylase by pinoxaden. PNAS 107:22072–22077PubMedGoogle Scholar
  174. Yu X, Liu Y, Li Y, Wang Q (2015) Design, synthesis, and acaricidal/insecticidal activities of oxazoline derivatives containing a sulfur ether moiety. J Agric Food Chem 63:9690–9695PubMedGoogle Scholar
  175. Zhang YY, Xu H (2017) Recent progress in the chemistry and biology of limonoids. RSC Adv 7:35191–35220Google Scholar
  176. Zhang L, Yan C, Guo Q, Zhang J, Ruiz-Menjivar J (2018) The impact of agricultural chemical inputs on environment: global evidence from informetrics analysis and visualization. Int J Low-Carbon Tech 13:338–352Google Scholar
  177. Zhao X, Cui H, Wang Y, Sun C, Cui B, Zeng Z (2018) Development strategies and prospects of nano-based smart pesticide formulation. J Agric Food Chem 66:6504–6512PubMedGoogle Scholar

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© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Departamento de Química da Faculdade de Filosofia, Ciências e LetrasUniversidade de São PauloRibeirão PretoBrazil
  2. 2.Dinagro Agropecuária Ltda.Ribeirão PretoBrazil

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