Haplophyllum

Quinoline alkaloids from the Rutaceae family (a = L-anthranilic acid) show antimicrobial activity. Moreover, quinoline alkaloids of the Haplophyllum species are known for their powerful biological properties. For example, skim-mianine has sedative, hypothermic and antidiuretic uses. Haplophyllidine is a strong depressant of the CNS. 

Nazrullaev, S. S., Bessonova, I. A. and Akhmedkhodzhaeva, K. S. 2001. Estrogenic activity as a function of chemical structure in Haplophyllum quinoline alkaloids. Chemistry of Natural Compounds, 31(6) 551-555. 

Non-hemiterpenoid Quinolines.—A re-examination of the alkaloids of Haplophyllum dubium resulted in the isolation of two members of the 2-aryl-4-quinolone group, i.e. graveoline (2 R = Me) and the new alkaloid norgraveoline (2 R = H).5 A new bacterial pseudan (3) has been obtained from Pseudomonas aeruginosa.8... 

Furoquinoline Alkaloids.—Glycohaplopine (1 R1 = H, R2 = O-glucosyl, R3 = OMe), a new alkaloid isolated from Haplophyllum perforatum, is believed to contain a /3-glycosidic link.6... 

Isolation and Spectroscopic Studies.—The Table (p. 79) records the isolation of new alkaloids and of alkaloids of established constitution obtained from new sources.2-16 The further investigation of Haplophyllum perforatum raises to nineteen the number of quinoline alkaloids found in this species. Another feature of isolation studies this year is the examination of four species of Myrtopsis. 

Choisya ternata Datura stramonium Haplophyllum perforatum... 

Non-hemiterpenoid Quinolines.—New sources of the simple quinolines 4-methoxy-l-methyl-2-quinolone and its 8-methoxy-derivative (folimine) have been reported the former was isolated from Myrtopsis sellingii9 and from Zanthoxylum cuspidatum,16 and folimine was shown to be a constituent of Haplophyllum perforatum.5 The latter species also contains foliosidine (9), previously isolated from H. foliosum. The micro-organism Pseudomonas aertiginosa has been shown to contain 2-(hept-l-enyl)-4-quinolone (12).10 The structure of the alkaloid was established by n.m.r. and mass spectroscopy and by its synthesis from aniline and the j3-keto-ester Me(CH2)4CH=CHC0CH2C02Me. 

Platydesmine (5 R = H), the biosynthetic precursor of dictamnine and other furoquinoline alkaloids, has been detected for the first time in a Haplophyllum species H. perforatum).5 Choisya ternata is known to contain O-methyl-balfourodinium salt (4 R = OMe), but now AT-methylplatydesminium salt (4 R = H) has been isolated in equal amount to (4 R = OMe) from the stalks and roots (4 R = OMe) is the predominant quaternary alkaloid of the leaves.3... 

X-Ray analysis of anhydroperforine (16) appears to establish the stereochemistry of the Haplophyllum alkaloid perforine (17).10 A related alkaloid, perfamine (18), reacts with methyl iodide at 250 °C to give an isodictamnine derivative (19).11... 

Monoterpenoid Quinoline Alkaloids.—The first examples of monoterpenoid quinoline alkaloids were isolated from Haplophyllum bucharicum some time ago, but the structures proposed on the basis of chemical and spectroscopic studies are not yet secure (cf. Vol. 1, p. 97 Vol. 2, p. 88 and Vol. 4, p. 119). The constitution... 

Haplophyllum, Melicope, Orixa spp., Ruta graveolens (Rutaceae) Semi-synthetic from Lysergamide ex ergot synthesized by Albert Hofmann (Swiss chemist, 1943) use advocated by Timothy Leary (US psychologist, 1960s)... 

Evodia merrillii, Ruta graveolens, Skimmia arborescens, S.japonica Dictamnus, Esenbeckia, Fagara, Glycosmis, Haplophyllum,... 

Aegle marmelos, Dictamnus angustfolius, Flindersia spp., Fagara coco, F. spp., Haplophyllum spp., anthoxylum spp. (Rutaceae)... 

A number of simple quinolines and quinolones have been isolated from various rutaceous plants, e.g., from angostura bark (Volume III, p. 80) and from Lunasia amara Blanco (Volume VII, p. 241 this chapter Section IV,A). The leaves of Haplophyllum dubium Eug. Kor (15, 16) contain dubamine (mp 96°-97°) which has been identified (17) as 2-(3,4-methylenedioxyphenyl)quinoline (I). Ruta graveolens L. contains, in addition to furoquinolines, the alkaloids graveoline (mp 205°) (18,19), and graveolinine (mp 115°-116°) (20), the latter (II) is also found in L. amara, and the former is the related l-methyl-4-quinolone (III). 

A somewhat more complex 4-methoxy-2-quinolone is the alkaloid foliosidine (VIII) (inp 141°-142°) from Haplophyllum foliosum Vved. (see Section VI). The 2,3-dihydroxyisopentyloxy side chain, also found in evoxine and maculosine, was shown to be present by periodic acid oxidation to acetone and an optically inactive aldehyde. 

Haplatine, Methylevoxine, and Perfamine. Haplophyllum species have continued to yield new furoquinoline alkaloids. 7-Isopentenyl-8-methoxydictamnine is a constituent of H. perforatum (c/. Vol. 6) and its oxidation product, haplatine (9), has now been isolated from H. latifolium acid hydrolysis furnishes haplopine (7-hydroxy-8-methoxydictamnine). Methylevoxine (10) was obtained from H. perforatum, but... 

The hydroxydihydropyranoquinolone (—)-ribalinine (47) is a constituent of the trunk and root bark of Araliopsis soyauxii f the (+ )-enantiomer (folifine) was obtained earlier from Haplophyllum species and the racemate, which has been synthesized was isolated from B. riedelianum. (-l-)-Isoplatydesmine (43) has also been isolated from A. soyauxii and can be regarded as a new alkaloid since isoplatydesmine obtained recently from Pelea barbigera (cf. Vol. 6) probably is the... 

A new alkaloid, haplobucharine from H. bucharicum, was shown by spectral studies to be the N-prenyl derivative (51) of another Haplophyllum alkaloid, khaplopholine (50). q... 

Flindersine Atlantia, Fagara, ° Haplophyllum, Micromelura,Zanthoxyllum °... 

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