Angelic Acid Research Articles

Studies on the constituents of the flower stalk of Petasites japonicus Maxim. VII. On the components of the volatile oil

The neutral volatile oil of the flower stalk of Petasites japonicus was separated by silica gel column chromatography and then by gas chromatography. Isopentanol, 3-hexen-1-ol, 1-nonen-3-ol, l-linalool, and veratrole were identified as the minor constituents. The volatile oils of the flower stalk collected from various places in Japan and oils extracted from various organs of the plant were examined (Table I). Large quantities of 1-nonene and angelic acid were found in any parts of the plant. The oil obtained from flower stalks consisted mainly of 1-undecene, 1-tridecene, 3-acetoxy-1-nonene, β-elemene, and β-bisabolene, and the oil from the leaves consisted mainly of 1-tridedene, β-caryophyllene, and alcohols.

A mass-spectrometric study of linear monohydroxy-and monoacyloxydihydrofurocoumarins

The mass spectra of the following six linear monohydroxy- and monoacyloxydihydrofurocoumarins have been studied: marmezin (I), [D]marmezin (II), O-acetylmarmezin (III), deltoin (IV), pranchimgin (V), and seseliflorin (VI). It has been shown that it is possible by the mass-spectrometric method of analysis to determine the molecular weights of the acids the acyl radicals of which are present in these substances, to distinguish the acyl radical of angelic acid from that of senecionic acid, and also to distinguish this class of compounds from the angular dihydrofurocoumarins and from the angular and linear dihydropyranocoumarins isomeric with them.

Die Wohl‐Ziegler‐Bromierung von Tiglin‐ und Angelika‐säureestern

AbstractThe Wohl‐Ziegler bromination (with N‐bromo‐succinimide = NBS) of methyl tiglate (1b) gave a 2:1 mixture of methyl γ‐bromotiglate (3b) and methyl β′‐bromotiglate (5b). This ratio of γ‐ to β′‐bromination was unaffected by changes of solvent, catalyst or size of the ester alkoxy group. The same products were obtained from the NBS treatment of methyl angelate (2b). This NBS‐bromination appears to be thermodynamically controlled, since both angelic and tiglic acid as well as their methyl esters were brought into equilibrium (1 ⇆ 2 = > 9:1) with catalytic amounts of NBS.

Studies on Constituents of Crude Drugs. I. Alkaloids of Symphytum officinale LINN.

Two pyrrolizidine alkaloids, symphytine (I), a new compound, and echimidine (II) have been isolated from the dried roots of Symphytum officinale. Both have a retronecine nucleus esterified on the 7-hydroxyl group with angelic acid. The other esterifying acid of symphytine is l-viridifloric acid (III), identical with the authentic sample. The structure of symphytine, a diastereoisomer of echiumine (retronecine esterified with angelic acid and trachelanthic acid), has been confirmed. A large amount of allantoin has also been isolated from the dried roots and leaves.

New coumarins isolated from the root of Peucedanum formosanum Hayata and Peucedanum japonicum Thunb

A new coumarin, peuformosin (I), C24H26O7, mp 155-156°, [α] 27D+67.3°, was isolated from ether extract of the root of Peucedanum formosanum HAYATA, in addition to (+)-anomalin, upon silica gel column chromatography, and was elucidated as 3'-angeloyloxy-4'-senecioyloxy-3', 4'-dihydroseselin from the fact that treatment of I with ethanolic sodium hydroxide under mild condition led to the formation of senecioic acid and 3'-angeloyloxy-4'-ethylkhellactone (VI) which yielded angelic acid and (+)-trans-ethylkhellactone (IIIc) upon further saponification. The ether extract of the root of Peucedanum japonicum THUNB. afforded a new coumarin, peucedanol (VII), C14H16O5, mp 174-175°, [α]20D+31.2°, and a crystalline compound (XI), C21H22O7, mp 90-96°. Peucedanol has three hydroxyl groups, one of which is phenolic. Oxidation of mono-O-methyl peucedanol (VIII) with sodium periodate yielded 6-formylmethyl-7-methoxycoumarin (X) with the formation of acetone, indicating that the structure of VII must be presented as 6-(2, 3-dihydroxy-3-methylbutyl)-7-hydroxycoumarin. The compound XI was presumed to be a mixture of acetyl-angeloylkhellactone (XIa) and acetyl- tigloylkhellactone (XIb) from NMR spectrum and the compsition of XI, and from the fact that treatment of XI with ethanolic sodium hydroxide yielded (±)-cis- (XIIb) and (±)-trans-ethylkhellactone (XIIa), and angelic, tiglic, and acetic acids.

Pyrrolizidine alkaloids. Biosynthesis of the angelate component of heliosupine.

[u-14C]-L-Isoleucine is specifically incorporated into the angelate component of heliosupine in Cynoglossum officinale L. The relationship between angelic acid and seneciphyllic acid biosynthesis is discussed.

A sesquiterpene lactone badkhysinin from the roots ofFerula oopoda

A sesquiterpene lactone with the composition C20H24O5, mp 104°–105° C, [α]D −212.4° C (alcohol) has been isolated from the roots ofFerula oopoda Boiss. and has been called badkhysinin. Badkhysinin is an ester of angelic acid and an epoxyhydroxylactone C15H18O4 with mp 185°–186° C apparently related to guaianolide with a hydrocarbon skeleton of irregular structure. A number of possible structural formulas for badkhysinin are given.

Piptoside, a novel alkali-labile glucoside from Piptocalyx moorei Oliv.

The β-D-glucopyranoside, piptoside, is cleaved by hot dilute acid to glucose and aglucone, the latter being partly converted with loss of carbon dioxide into a furan keto acid. Glucose is also liberated by the action of bases. With sodium methoxide, the aglucone residue rearranges to a pair of isomeric dilactone esters, whereas, with aqueous sodium hydroxide, fission of the carbon chain to (-)-2,3-dimethylsuccinic acid occurs; with alkaline hydrogen peroxide, oxidative chain fission yields a buty- rolactone-4,4-dicarboxylic acid. The structure and partial stereochemistry of each of the products follows from chemical and spectroscopic information. These results, as also those of periodate oxidation, are accounted for by formulation of the aglucone as a system of two spiro-joined γ-lactone rings, one of which is fused to a ketofuranose ring. The reaction products are analogous to well-known products from simple sugars. The hemiacetal hydroxyl group of the ketofuranose remains free in the glucoside and is unusally acidic towards diazomethane, the methyl derivatives not being alkalilabile.��� Biogenesis of the aglucone may follow Michael-type addition of a 3-dehydrohexonic acid (of unknown stereochemistry) to angelic acid, or some variant.

Xanthogalin — A new coumarin fromXanthogalum purpurascens Lallem.

A new Coumarin C19H20O5, designated xanthogalin, has been isolated from the roots ofXanthogalum purpurascens. It is an ester of a new hydroxycoumarin, xanthogalol C14H14O4, andtrans-1, 2-dimethylacrylic (angelic) acid.

Studies on biliary excretion in the rabbit. II. The relationship between the chemical structure of certain natural or synthetic pentacyclic triterpenes and their icterogenic activity. 1. The substituents on carbon atoms 3, 17, 22 and 24.

Considerable interest has been aroused by the use of the pentacyclic triterpene acid, icterogenin, in studies associated with bilirubin excretion and the genesis of icterus of the intrahepatic cholestasis type. This compound, which produces within a few hours after administration to sheep and rabbits a very marked decline in bile flow and the amount of bilirubin excreted hourly without any histological damage to the liver parenchyma visible in the ordinary light microscope, has proved to be very useful in the study of the South African ovine photosensitization disease known as 'geeldikkop’ (‘yellow thick head’). In connexion with research on this disease, a study of the relationship between the chemical structure of the pentacyclic triterpenes and their icterogenic activity is in progress. The first part of this work dealing with certain structural variations in triterpenes of the oleanane and 24-noroleanane (hedragane) series is reported in this paper. Assays are recorded of sixteen of these compounds and some of their derivatives for such activity, using a modification of the rabbit test described in the first paper of this series (Heikel, Knight, Rimington, Ritchie & Williams 1960). Four new icterogenic agents are discussed, namely: 22 β -angeloyloxyoleanolic acid, 22 β -angeloyloxyhedragolic acid, 22 β -angeloyloxy-24-hydroxyoleanolic acid and 22 β -angeloyloxy-24-oxo-oleanonic acid. The first two mentioned compounds are extremely active, their potency far surpassing that of icterogenin. Icterogenic activity of these acids appears, so far, to be based upon the presence of a β -equatorially orientated hydroxyl group at C(3) or a hydroxyl at C(24) and a 22 β -angeloyl side-chain on the triterpene molecule. Stereoisomer specificity is shown in respect of icterogenicity by these compounds since the epimers of two of these substances carrying α -axially orientated hydroxyls at C(3) have been shown to have no such effect on bile flow or bilirubin excretion. Removal of the angelic acid side-chain, substitution of the hydroxyl groups or replacement of these with a ketone function, is followed by loss of activity.

Coumarins I: Isolation, Purification, and Structure Determination of Pteryxin and Suksdorfin

Pteryxin and suksdorfin were isolated from petroleum ether extracts of Pteryxia terebinthina (Hook.) Coulter and Rose var. terebinthina and Lomatium suksdorfii (Wats.) Coulter and Rose, respectively. A suitable chromatographic procedure was developed for their purification. Upon hydrolysis, these coumarins yielded the same isomeric alcohols obtained from visnadin and samidin. In addition, an alcohol and its acetate which had not been reported previously were obtained and assigned the structures (+)-cis-ethylkhellactone and (−)-cis-acetylethylkhellactone. Pteryxin, during the hydrolysis, yielded angelic and acetic acids. Quantitative hydrolytic studies, optical rotations, isolation of the partially hydrolyzed coumarins as acetates, and ultraviolet and infrared absorption studies led to the establishment of the following structure for pteryxin: 3′-acetyl-4′angeloyl-(+)-cis-khellactone; and for suksdorfin: 3′-acetyl-4′-isovaleryl-(+)-cis-khellactone. The probable conformation of these substances is discussed.

Studies on the Constituents of Umbelliferae Plants. VI. Studies on the Constituents of Angelica edulis MIYABE. (2).

The structure of edultin (I), which was isolated from the root of Angelica edulis MIYABE was investigated. The acidic fraction obtained by hydrolysis of (I), was found to be a mixture of acetic acid and angelic acid. By hydrolysis of (I) under various conditions, (II)∼(V), and (VI) were identified as the neutral fraction. The complete structure of edultin was established as 8-(1-acetyloxyisopropyl)-9-angeloyloxy-2H-[2, 3-h]-1-benzopyran-2-one.

Notes. Long Range Splittings in the NMR Spectra of Isomeric 2-Bromo-2-butenes

The recent publication of Fraser on long-range coupling between the protons in the methyl groups of tiglic and angelic acids and their methyl esters prompts us to report a similar observation in the NMR spectra of cis- and trans-2-bromo-2-butene. In this case, also, we observe coupling between the methyl group protons that are separated from one another by five bonds (four single bonds and one double bond). Furthermore, the magnitude of this coupling is larger when the two methyl groups are trans disposed about the olefinic linkage than when they are cis oriented. The possibilities of such splittings have been alluded to previously to account for the barely perceptible fine structure in one of the peaks in the NMR spectrum of methyl photosantonate. Such splittings across five bonds have also been observed in the NMR spectra of plumericin and in the spectra of other butene derivatives.

セリ科植物の生薬学的研究 第18報

Four kinds of coumarin derivatives were isolated from Angelica Keiskei KOIDZUMI (Umbelliferae) by the process shown in Chart 1, these being psoralen (I), m. p. 161-162°, angelicin (II), m. p. 139-140°, bergapten (III), m. p. 187.5-188.5°, and xanthotoxin (IV), m. p. 146-147°. Besides these, angelic acid (V), m. p. 47-48°, and behenic acid (VI), m. p. 75-76°, were obtained as acid substances. Good results were obtained by the use of silica-gel chromatography for isolation of each of these substances but no new derivative of coumarin was obtained. Psoralen had hitherto been isolated from Leguminosae, Moraceae, and Rutaceae plants, and Hata and others had isolated it from the root of Angelica japonica A. GRAY among the Umbelliferae plants. The present result seems to suggest that psoralen might be distributed widely in the Umbelliferae plants also.

Principles of Peucedanum japonicum THUNB. II. Studies on P-Acid.

The p-acid, which was isolated from Peucedanum japonicum THUNB., was proved to be a mixture of senecioic acid, angelic acid, and a small amount of unidentified compound. Gas chromatography, ozone oxidation, NMR spectrography, and paper chromatography were used for its identification. Senecioic acid was also identified as p-bromo- and p-phenyl-phenacyl esters.

Notes: The Synthesis of Esters of Angelic Acid

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNotes: The Synthesis of Esters of Angelic AcidS. Morris Kupchan and Adriano AfonsoCite this: J. Org. Chem. 1960, 25, 12, 2217–2218Publication Date (Print):December 1, 1960Publication History Published online31 March 2003Published inissue 1 December 1960https://doi.org/10.1021/jo01082a602RIGHTS & PERMISSIONSArticle Views292Altmetric-Citations24LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (274 KB) Get e-Alerts Get e-Alerts

LONG-RANGE COUPLING CONSTANTS IN THE N.M.R. SPECTRA OF OLEFINES

The spectra of tiglic and angelic acids and their methyl esters have been determined and analyzed by first-order perturbation theory. The magnitudes of the long-range coupling constants were found to be greater in each instance for trans oriented hydrogens than for cis hydrogens. All long-range coupling constants already reported have been examined and found to be consistent with the proposal that trans coupling constants are larger than cis coupling constants for hydrogens separated by more than three bonds.

165. The crystal and molecular structures of tiglic and angelic acids. Part II. Angelic acid

165. The crystal and molecular structures of tiglic and angelic acids. Part II. Angelic acid

164. The crystal and molecular structure of tiglic and angelic acids. Part I. Tiglic acid

164. The crystal and molecular structure of tiglic and angelic acids. Part I. Tiglic acid

Some active substances from Petasites officinalis Moench. I. Petasin and petasolesters B and C

Three spasmolytically active substances which contain no nitrogen, namely petasin and the petasolesters B and C, were isolated fromPetasites officinalis Moench. They are all esters of the same C15-alcohol. Petasin is an ester of angelic acid, whereas the petasolesters B and C are derivates of a new acid containing sulphur, theβ-methylmercapto-acrylic acid.