Concise, efficient new synthesis of pipercide, an insecticidal unsaturated amide from Piper nigrum, and related compounds

Strunz, George M.; Finlay, Heather J.

doi:10.1016/s0040-4020(01)89414-x

Cited by 29 publications

(21 citation statements)

References 12 publications

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“…Pellitorine 1 As a result of the present study and previous work (6,7), more than a dozen unsaturated amides, mostly alkaloids from various Piper spp., are readily accessible and several are presently being assayed for insecticidal activity against such economically important insect pests as spruce budworm (Choristoneurafilmiferaiza), gypsy moth (Lymantria dispar), and forest tent caterpillar (Malacosorna disstria).…”

Section: C Homologation Amidationsupporting

confidence: 74%

“…The insecticidal and other biological properties of some unsaturated amides, e.g., piper-oride. Addition of a glycol (preferably 1,3-propane dial (6)) then produced an acetal I1 (x = 4), which underwent fragmentation affording the glycol ester intermediate 111 (x = 4), with exclusively E geometry about the double bond. The methodology has proved to be eminently suitable for the synthesis of Piper amides such as 2 and 3 (rn = 7), which were prepared via direct amidation of the versatile intermediate 111 (x = 4).…”

Section: Introductionmentioning

confidence: 99%

“…The corresponding nor-piperamides (rn = 6 or 10) are accessible, if cyclopentanone is substituted for the six-membered ketone (6). The susceptibility of the processes occurring in the course of the aldol condensation -fragmentation sequence to subtle steric and stereoelectronic effects raises interesting questions about the scope of the methodology, e.g., when other sized cyclic ketones (cylobutanone, cycloheptanone etc.)…”

Section: Introductionmentioning

confidence: 99%

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Expedient synthesis of unsaturated amide alkaloids from Piper spp: Exploring the scope of recent methodology

Strunz¹,

Finlay²

1996

Can. J. Chem.

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The Sakai aryl aldehyde -cyclic ketone aldol -Grob fragmentation sequence was extended to cinnamaldehyde and cyclohexanone, and the product was elaborated to analogues of the alkaloid piperstachine. The effects of substituents on the reaction involving cinnamaldehyde were studied. The aldol-fragmentation sequence failed with benzaldehyde when cyclooctanone or cyclobutanone was substituted for cyclohexanone or cyclopentanone, and the reasons for this failure were examined. Four-carbon Wittig homologation of the piperonalxyclobutanone aldol-fragmentation product, a hypothetical route to alkaloids such as retrofractamide A, was thus not viable. Instead, three-carbon homologation of the readily available piperonalxyclopentanone product, using alkyne chemistry recently disclosed by Lu and Trost, afforded these alkaloids in excellent overall yield. The alkyne isomerization was also used to effect efficient syntheses of pellitorine and several other nonaromatic 2E,4E-dienoic Piper amide alkaloids.Key words: Piper; amides, alkaloids, insecticides, aldol, fragmentation, cinnamaldehydes, alkyne, redox, isomerization.RCsumk : La stquence de Sakai, qui peut consister en une reaction d'aldol entre un aldehyde et une cetone cyclique suivie d'une fragmentation de Grob, fut utiliske pour preparer des analogues de l'alcalo'ide piperstachine B partir du cinnamaldehyde et de la cyclohexanone. L'influence des substituants sur la reaction du cinnamaldthyde furent tgalement ttudiees. La sequence aldol fragmentation entre le benzaldthyde et la cyclooctanone ou la cyclobutanone ne fonctionne pas malgrt que la cyclopentanone et la cyclohexanone produisent le resultat anticipk. Ce resultat fut CtudiC en detail. Le produit obtenu B paritr de la cyclobutanone, suite i i une homologation de Wittig de quatre carbones, aurait ainsi donne accbs aux alcalo'ides tels la rtfractamide A. Cependant, une homologation de trois carbones sur le produit de la skquence de Sakai entre le pipkronal et la cyclopentanone fournit ces alcalo'ides en d'excellents rendements en utilisant la chimie acttylenique dkveloppt rtcemment par Lu et Trost. L'isomerisation acttylenique fut aussi employte pour la synthbse de la ptllitorine et plusieurs autres alcalo'ids amidiques non-aromatiques 2E,4E-dienoiques des espbces Piper.

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Section: C Homologation Amidationsupporting

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Expedient synthesis of unsaturated amide alkaloids from Piper spp: Exploring the scope of recent methodology

Strunz¹,

Finlay²

1996

Can. J. Chem.

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“…Sumathykutty and Madhusudana (1999) reported that some oil like compounds present in pepper are very effective to control Phomopsis vsexans. Strunz and Finlay (1994) synthesized pipercide a pesticidal unsaturated amide from black pepper fruit. Weaver and Neale (1988) studied the method for determination of piperine from black pepper fruit and they found that piperine present in black pepper fruit extract.…”

Section: Introductionmentioning

confidence: 99%

Isolation and characterization of piperine from the fruits of black pepper (Piper nigrum)

Saha

Seal

Noor

2014

J Bangladesh Agric Univ

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Black pepper (Piper nigrum) is a spice vine crop which is used as a food preservative and as an essential component in traditional medicines. The aim of this study was to extract, isolate and characterize the structure of piperine. The fruits of black pepper were extracted in ethanol and compounds present identified by TLC under iodine vapour. A compound (A 2 ) having R f value 0.54 was isolated by column chromatography which may be responsible for the pungency of black pepper. After recrystallization of the isolate with benzene and chloroform mixture (7:1) gave pale yellow crystals of m.p. 128~129 o C (reported 130 o C). The IR, 1 H NMR and mass spectra of the pure crystalline compound (A 2 ) were recorded. The mass spectra of the compound (A 2 ) showed molecular ion peak M +· at 284.5 which was similar to that of piperine (mol. wt. 285).

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“…Plantas da família Piperaceae constituem uma fonte de isobutilamidas insaturadas de cadeia longa, com propriedades inseticidas, como a piperina encontrada na Piper nigrum L. (pimenta-do-reino) (Strunz & Finlay, 1994). Estrela et al (2005) pesquisaram as amidas análogas a piperina, com os grupos N-hexil, N-isopropil e N-isopentil ligados ao isopentil (3,4-metilenodioxifenil) amida.…”

Section: Introductionunclassified

Atividade inseticida do óleo essencial de pimenta longa (Piper hispidinervum C. DC.) sobre lagarta-do-cartucho do milho Spodoptera frugiperda (J. E. Smith, 1797) (Lepidoptera: Noctuidae)

Lima

Cardoso²,

Moraes³

et al. 2009

Acta Amaz.

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RESUMOOs objetivos desta pesquisa foram a obtenção e caracterização do óleo essencial de folhas de pimenta longa Piper hispidinervum, e avaliação de seu efeito no comportamento e/ou mortalidade da lagarta-do-cartucho do milho Spodoptera frugiperda. O óleo essencial foi obtido pela técnica "arraste a vapor d'água", utilizando-se de um aparelho de Clevenger modificado, e posteriormente submetido, à análise por CG-EM e CG. Foram realizados testes de ingestão e contato tópico em lagartas de 1° e 3° ínstar. Os resultados constataram que o óleo essencial de pimenta-longa possui atividade inseticida sobre S. frugiperda, causando redução alimentar e mortalidade, sendo o safrol (82%) seu constituinte majoritário. Verificou-se mortalidade no teste de ingestão em lagartas de 1° ínstar com CL 50 = 16,2 mg/mL e para lagartas de 3° ínstar a CL 50 = 9,4 mg/mL com redução alimentar CD 50 = 0,72 mg/mL; e de toxicidade aguda no teste de contato tópico com DL 50 = 277,91 μg/lagarta, após o intervalo de tempo de 96 horas, sendo também observados sintomas de neurotoxicidade, como o efeito knock-down. PALAVRAS-CHAVE:Lagarta-do-cartucho, Safrol, Manejo integrado de pragas.Insecticidal Activity of Long-pepper essential oil (Piper hispidinervum C. DC.) on fall armyworm Spodoptera frugiperda (J. E. Smith, 1797) (Lepidoptera: Noctuidae) ABSTRACT The objectives of this research were to evaluate the chemical composition and bioactivity of the essential oil from the longpepper leaves (Piper hispidinervum) and its effect on the comportment and/or mortality of the fall armyworm (Spodoptera frugiperda). The essential oil was obtained by steam stream distillation, using the modified Clevenger apparatus, the chemical composition was analyzed by GC-MS and GC. Tests of ingestion and topical application in fall armyworm of 1 st and 3 rd ínstar were made. The results showed that the long-pepper essential oil has insecticide activity on S. frugiperda, causing mortality and food reduction, and safrole (82%) as its majority constituent. Mortality was found in the ingestion test in larvae of 1 st ínstar LC 50 = 16.2 mg/mL for larvae of 3 rd ínstar LC 50 = 9.4 mg/mL, with reduced food CD 50 = 0.72 mg/mL; and acute toxicity test of the contact topic with LD 50 = 277.91 μg/larvae, after an interval of 96 hours, neurotoxicity symptoms were also observed, as knock-down effect.

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Concise, efficient new synthesis of pipercide, an insecticidal unsaturated amide from Piper nigrum, and related compounds

Cited by 29 publications

References 12 publications

Expedient synthesis of unsaturated amide alkaloids from Piper spp: Exploring the scope of recent methodology

Expedient synthesis of unsaturated amide alkaloids from Piper spp: Exploring the scope of recent methodology

Isolation and characterization of piperine from the fruits of black pepper (Piper nigrum)

Atividade inseticida do óleo essencial de pimenta longa (Piper hispidinervum C. DC.) sobre lagarta-do-cartucho do milho Spodoptera frugiperda (J. E. Smith, 1797) (Lepidoptera: Noctuidae)

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