Über die Inhaltsstoffe des schwarzen Pfeffers

Grewe, Rudolf; Freist, Wolfgang; Neumann, Helge; Kersten, Siegfried

doi:10.1002/cber.19701031204

Cited by 65 publications

(28 citation statements)

References 15 publications

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“…It was presumed from the UV data as shown in Table I that a 2E,4E configuration in a diene system would be present in compound 4 (piperine, ~max 340 nm), a 2Z,4Z configuration in I (chavicine, Imax 3 18 nm), a 2E,4Z or 2Z,4E configuration in 2 and 3 (isochavicine or isopiperine, Imax 329 and 335 nm). The UV data were in agreement with those of synthesized piperine isomers reported in the literature (Grewe et al, 1970;Yamamoto et al, 1974;De Cleyn & Verzele, 1975a,b). The detailed structural elucidation for 1, 2, 3 and 4 was determined on the basis of NMR experiments.…”

Section: Methodssupporting

confidence: 90%

“…The detailed structural elucidation for 1, 2, 3 and 4 was determined on the basis of NMR experiments. IH-lH NOE and C/H COSY were measured, in order to recognize the reported IH assignments (Grewe et al, 1970;Wenkert et al, 1971;Yamamoto et al, 1974;De Cleyn & Verzele, 1975a, b;Tsuboi et al, 1984) and to assign the 13C signals in the spectra 125. 2, 3 and 4.…”

Section: Methodsmentioning

confidence: 99%

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Photochemical Isomerization of Piperine, a Pungent Constituent in Pepper.

Hashimoto

Yaoi

Koshiba

et al. 1996

FSTI

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A separation method for piperine and its isomers (chavicine, isochavicine and isopiperine) from a photoirradiated mixture of piperine, in solution and in suspension, by high performance liquid chromatography (HPLC), was investigated to clarify the relationship between the disappearance of the pungency in older, ground pepper and the photoisomerization of piperine. Piperine and its isomers were separated on a Sumichiral OA-2000 column with hexane/dichloromethane/ethanol (4811610.8) as an eluting solvent. Their structural elucidation was carried out using nuclear magnetic resonance spectroscopy and HPLC atmospheric pressure chemical ionization mass spectrometry (LC/APCIMS). Although the increment in the three isomers in commercial ground pepper after exposure to sunlight was observed by monitoring the MH+ ion on LC/APCIMS, the degree of increase varied very little. It is questionable whether the disappearance of the pungency in older, ground pepper is derived from the formation of tasteless isomers by photochemical changes in piperine.

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Section: Methodssupporting

confidence: 90%

Section: Methodsmentioning

confidence: 99%

Photochemical Isomerization of Piperine, a Pungent Constituent in Pepper.

Hashimoto

Yaoi

Koshiba

et al. 1996

FSTI

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“…The 2,4-dienoate was prepared by condensation of the aldehyde with the phosphonate in the presence of sodium methoxide, whose configurations were predominantly trans at C-2 and exclusively trans at C-4. The protecting group of the 2,4-dienoate was removed by p-toluenesulfonic acid or tosic acid (p-TsOH) in MeOH to give (2E,4E)-methyl 10-hydroxy-2,4-decadienoate, which was oxidized with pyridinium chlorochromate to (2E,4E)-methyl 10-oxo-2,4-decadienoate.The piperonyl moiety, piperonyl alcohol, was brominated with phosphorus tribromide (PBr 3 ) to give piperonyl bromide in quantitative yield, which was converted to 3,4-methylenedioxybenzyl-triphenylphosphonium bromide(93% yield) with triphenylphosphine according to the method of Grewe et al (1970). The phosphonium bromide in benzene was converted with an equimolar amount of n-butyllithium (n-BuLi) in n-hexane solution to the Wittig reagent, which was coupled in situ with an equimolar amount of (2E,4E)-methyl 10-oxo-2,4-decadienoate to give the condensation product in 70% yield.…”

Section: Total Synthesis Of Pipercidementioning

confidence: 99%

“…Treatment of this product with oxalyl chloride and acylation of 1,2-methylenedioxybenzene in the presence of stannic chloride gave the Friedel-Crafts acylation product, methyl ω-piperonoyloctanoate. NaBH 4 reduction of the keto-ester, followed by dehydration and hydrolysis gave piperolein B acid which was known (Grewe et al, 1970). LiAlH 4 reduction of the acid followed by CrO 3 /Py oxidation gave the corresponding aldehyde which was subjected to Wittig reaction with γ-triphenylphosphorane methyl crotononate to give 20% all-trans methyl guineensate.…”

Section: Total Synthesis Of Guineensinementioning

confidence: 99%

Piperine-Type Amides: Review of the Chemical and Biological Characteristics

Okwute¹,

Egharevba²

2013

IJC

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A new group of alkaloids emerged in 1819 following the isolation of piperine from the fruits of Piper nigrum. Since then, a large number of these compounds now referred to as piperine-type alkaloids or alkamides or piperamides have been isolated commonly from species belonging to the genus piper (piperaceae) which have worldwide geographical distribution. As a result of the traditional uses of piper species as spices in foods and in phytomedicines globally a number of their extractives and indeed the constituent amides have been screened for pharmacological properties. The biogenesis of the amides has been investigated and a number of synthetic pathways have been developed to make them readily available for biological studies. It has now been established that piperine and its analogues are potential pesticides and possess a number of medicinal properties. They are regarded as universal enhancers in pesticide and drug formulations. This review enhances our knowledge of these amides and paves way for further work.

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“…On the other hand, synthesis of guineensine 5 (piperamide-B13:3(2E,4E,12E)) from P. guineense (1 1) or piperolein B (piperamide-A9: l(8E)) from P. nigr~lrn (12) dictates an aldol condensation -fragmentation involving cyclooctanone and piperonal.…”

Section: Introductionmentioning

confidence: 99%

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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Über die Inhaltsstoffe des schwarzen Pfeffers

Cited by 65 publications

References 15 publications

Photochemical Isomerization of Piperine, a Pungent Constituent in Pepper.

Photochemical Isomerization of Piperine, a Pungent Constituent in Pepper.

Piperine-Type Amides: Review of the Chemical and Biological Characteristics

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

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