A new C-glucoside from <Emphasis Type="Italic">Commelina communis</Emphasis>

A new C-glucoside, 3,4-epoxy-5-hydroxymethyl benzoate 2-C-β-glucoside (1), together with a known alkaloid, 1H-indole-3-carbaldehyde (2), were isolated from the whole plant of Commelina communis L. The structures of these compounds were determined by 1D, 2D NMR and MS techniques. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 51–52, January–February, 2009.     

A new hydroquinone diglucoside from <Emphasis Type="Italic">Lysimachia fordiana</Emphasis>

A new hydroquinone diglucoside along with five known compounds was isolated from the whole plant of Lysimachia fordiana Oliv. The structure of the new compound was determined to be 2-heptyl-6-methoxy-1,4-hydroquinone-1,4-di-O--D-glucopyranoside (6). The five known compounds were identified as pentacosane (1), stigmasterol (2), 2-heptyl-6-methoxy-1,4-benzoquinone (3), palmitic acid (4), and rutin (5), respectively. This is the first report of the isolation of Lysimachia fordiana Oliv. in the family Primulaceae.Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 377–379, September–October, 2004.     

Metabolites of the marine fungus <Emphasis Type="Italic">Humicola fuscoatra</Emphasis> KMM 4629

A new sesquiterpene of the caryophyllene series, fuscoatrol A (1), and known compounds, 11-epiterpestacin (2) and -nitropropionic acid (3), were isolated from the marine fungus Humicola fuscoatra (Traaen) KMM 4629 associated with the Kuril colonial ascidium. The structure of 1 was established on the basis of X-ray diffraction data and 2D NMR spectroscopy. The antimicrobial and cytotoxic activities of compounds 1–3 were studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2534–2537, November, 2004.     

Cytotoxic activity of alkyl benzoate and fatty acids from the red sea sponge Hyrtios erectus

The chemical investigation of the methylene chloride fraction of marine sponge Hyrtios erectus led to the isolation of the known oxysterol (2) along with a new alkyl benzoate compound identified by spectroscopic methods (NMR and MS) as 4′-methylheptyl benzoate (1), whilst the n-butanol fraction afforded the known indole 3-carbaldehyde and β-carboline derivatives. Moreover, the hexane fraction was analysed by GC–MS for their fatty acids (FAs). A total of 17 FAs with chain lengths between 14 and 25 carbons were identified. Methyl-branched FAs are predominated suggesting the presence of bacterial symbionts in the H. erectus sponge. Furthermore, compounds 1 and 2 displayed significant cytotoxicity against breast adenocarcinoma (MCF-7) with IC₅₀ values of 2.4 and 3.8 μM, respectively, since compound 2 was also shown to have potent cytotoxic effect against hepatocellular carcinoma cells (HepG 2) with IC₅₀ value of 1.3 μM.     

The synthesis of 4-(2,6,10-trimethyl-1,3,5,9-undecatetraenyl)benzoic acid based on alkoxy alkene-acetal condensation

4-(2,6,10-Trimethyl-1,3,5,9-undecatetraenyl)benzoic acid (1) was synthesized starting from ethyl 4-formylbenzoate (2) and linalool. The key intermediate, ethyl 4-(2-methyl-3-oxo-1-propenyl)benzoate (5), was obtained by the addition of diethyl acetal (3), prepared from2, to ethyl 1-propenyl ether (EPE) followed by the hydrolysis of the resulting adduct.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 914–915, May, 1993.     

A new flavonol derivative from <Emphasis Type="Italic">Fagopyrum dibotrys</Emphasis>

A new flavonol derivative 3, 8-dihydroxy-10-methoxy-5-H-isochromeno[4, 3-b]chromen-7-one (1) together with four known compounds, glutinone (2), luteolin (3), acacetin 7-O-α-L-rhamnopyranosyl- (1→6)-β-D-glucopyranoside (4), and rutin (5) were isolated from the dried roots of Fagopyrum dibotrys. Their structures were determined by UV, IR, MS, ¹H, and ¹³C NMR spectroscopic analysis, including 2D NMR. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 567–568, November–December, 2008.     

Triterpene Glycosides from Cussonia paniculata. I. Isolation and Structure Determination of Glycosides A, B1, B2, C, D, G2, H1, and H2 from Leaves of Cussonia paniculata

The 3-O-β-D-glucopyranoside of β-sitosterol (1) and the known triterpene glycosides 3-O-α-L-arabinopyranosides of oleanolic (2a) and ursolic (2b) acids and hederagenin (3), 3-O-β-D-glucopyranosyl-(1→2)-α-L-arabinopyranosideofoleanolic acid (4), 3-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosides of oleanolic (5a) and ursolic (5b) acids and the newglycoside 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranoside of 23-hydroxyursolic acid (6) were isolated from leaves of Cussonia paniculata (Araliaceae). Their structures were established using chemical methods and NMR spectroscopy.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 160–163, March–April, 2005.     

Three antibacterial compounds from the roots of <Emphasis Type="Italic">Pteris multifida</Emphasis>

A new eudesmane-type sesquiterpenoid, 3β-caffeoxyl-1β,8α-dihydroxyeudesm-4(15)-ene (1), together with two known compounds including ludongnin V (2) and isoneorautenol (3), were isolated from the roots of Pteris multifida. Their structures were determined by spectral and chemical methods, with their antibacterial activities being evaluated by the microdilution technique, respectively. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 41–43, January–February, 2009.     

Studies on the constituents of the green alga <Emphasis Type="Italic">Ulva lactuca</Emphasis>

Phytochemical investigations on a marine green alga Ulva lactuca led to the isolation of two new compounds (E)-6-heptacosen-5-one (1) and (E)-6-octadecen-5-ol (2), along with four known compounds, (Z)-10-hexacosene (3), docosanoic acid (4), palmitic acid (5), and isofucosterol (6). Compounds 3 and 4 were isolated for the first time from this species. The structures of the compounds were deduced with the help of modern spectroscopic techniques.     

Bisabocurcumin, a new skeleton curcuminoid from the rhizomes of Curcuma longa L.

A new skeleton bisabolane-type sesquiterpene curcuminoid,bisabocurcumin(1),along with 5 known compounds,curcumin(2), demethoxycurcumin(3),bidemethoxycurcumin(4),(1E,4E)-1,5-bis(4-hydroxy-3-methoxyphenyl)-penta-1,4-dien-3-one(5),and (1E,4E)-1-(4-hydroxy-3-methoxyphenyl)-5-(4-hydroxy phenyl-)-penta-1,4-dien-3-one(6)were isolated from the rhizomes of Curcuma longa L.Their structures were determined on the basis of spectroscopic analysis.Bisabocurcumin(1) is firstly obtained from nature with a new skeleton combined by a bisabolane-type sesquiterpene and a 1,7-diphenylheptanoid through a C-C bond.     

New thiazinediones and other components from Xanthium strumarium

Two new thiazinediones along with five known compounds were isolated from the fruits of Xanthium strumarium L. The structures of the two new compounds were determined to be 7-hydroxymethyl-8,8-dimethyl-4,8-dihydrobenzol[1,4]thiazine-3,5-dione-11-O-β-D-glucopyranoside (1) and 2-hydroxy-7-hydroxymethyl-8,8-dimethyl-4,8-dihydrobenzol[1,4]thiazine-3,5-dione-11-O-β-D-glucopyranoside (2). The five known compounds were identified as xanthiazone (3), chlorogenic acid (4), ferulic acid (5), formononetin (6), and ononin (7), respectively. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 456–458, September–October, 2006.     

Herstellung von 6,14-Ethenomorphinan-Derivaten

Zusammenfassung Dihydronorthevinon (2b) wurde aus Dihydrothevinon (2a) mit Azodicarbonsäurediethylester (DEAD) hergestellt und zu einigen neuen N-substituierten Dihydronorthevinon-Derivaten (2c–2g) umgesetzt. Es wurdenGrignard-Reaktionen dieser Verbindungen mit Methylmagnesiumiodid bzw.tert-Butylmagnesiumchlorid durchgeführt. O-Demethylierungen von3a–3j ergaben die entsprechenden N-substituierten Buprenorphin- bzw. Diprenorphin-Analoga4a–4j.

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Preparation of 6,14-ethenomorphinan derivatives

Summary Dihydronorthevinone (2b) was prepared from dihydrothevinone (2a) with diethyl azodicarboxylate (DEAD) and transformed into a number of new N-substituted dihydronorthevinone derivatives (2c–2g).Grignard reactions of the new compounds with methylmagnesium iodide andtert-butyl-magnesium chloride were studied. O-Demethylation of3a–3j resulted in the corresponding N-substituted buprenorphine and diprenorphine analogs4a–4j.

     

Zur Kenntnis der Reaktionsfähigkeit des unsubstituierten Thiomorpholins und alkylsubstituierter Thiomorpholine, 5. Mitt.

The syntheses of 4-amino-thiomorpholine-1,1-dioxide (12) and 4-hydroxythiomorpholine-1,1-dioxide (11) from 1,4-thioxane-1,1-dioxide (1) by pressureless reaction of1 with hydrazine hydrate and hydroxylamine, resp. is described. In analogy various other N-substituted thiomorpholine-1,1-dioxides are obtained with prim. amines (2–8) and diamines (9, 10).12 condensates with aldehydes (14–24) and ketones (25–29); reaction of12 with1 gives N,N-dithiomorpholine-1,1-dioxide (13). Acylation of12 with monochlorides (30–35), dichlorides of dicarboxylic acids (36–40) and carboxylic acid anhydrides (41–43) proceeds smoothly. Compounds38–43 are cyclic imides. Isocyanates give with12 the expected compounds45–48.12 reacts with chlorinated 1,3,5-triazines to compounds which can be purified only with difficulty (49–51). Quaternization of the N-substituted thiomorpholine-1,1-dioxides with benzylbromide (52, 53) and methyliodide (54, 55) is possible. Ethylenbromide reacts with9 to give the bis quaternization product56. Further reactions of thiomorpholine-1,1-dioxide (57) with sulfuryl chloride (58), bromo cyanide (59), allylic chloride (60), chloro acetonitrile (61) and trityl chloride (62) are described.11 reacts with carboxylic acid chlorides (63–65) and iso-cyanates (66–70) to yield the expected compounds. Propylene oxide gives with12 the addition product71; sulfur dioxide is added to11 to thiomorpholine-1,1-dioxide sulfonic acid (72).

Teil der Diplomarbeit vonMartin Irmgard, Technische Hochschule Aachen. 1975.     

Arjunolic Acid Derivative Glycoside from the Stems of <Emphasis Type="Italic">Hedera colchica</Emphasis>

Five triterpenoid saponins were isolated from the stems of Hedera colchica K. Koch (Araliaceae). Two of them are new natural substances. HCS-A (1): 3-O-α-L-arabinopyranoside, 28-O-α-L-rhamnopyranosyl-(1→ 4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl-arjunolic acid. HCSt-B (2):3-O-β-D-xylopyranoside, 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl-hederagenin. A derivative of arjunolic acid is described for the first time in the Araliaceae family. The chemical structures of isolated compounds were established on the basis of chemical and 1D and 2D NMR experiments.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 39–41, January–February, 2005.     

Zur Kenntnis der Reaktionsfähigkeit des unsubstituierten Thiomorpholins und alkylsubstituierter Thiomorpholine. 3. Mitt

A new synthesis of thiomorpholine by ring closure of -chloro--aminodiethylene-sulfide with potassium hydroxide is reported. Numerous reactions of thiomorpholine (1) and, especially, 2-methyl-3-ethyl-thiomorpholine (2) are described such as acylation, diacylation (3–43), reactions with sulfonic acid chlorides (44–52), isocyanates (53–61, 70–75), diisocyanates (62–66, 76–78) and isothiocyanates (67–69, 79–82), alkylation reactions (83–111) and the synthesis of thiomorpholino-dithiocarbamates (112–121).

Teil der Dissertation,E. Wilms, Techn. Hochschule Aachen, 1971.     

Preparation and steric structure of 3(2H)-pyridazinones and 1,2-oxazin-6-ones fused with three- to six-membered saturated carbocycles or norbornane skeleton

Summary Reactions ofcis-2-(4-methylbenzoyl)-cyclopropane- (1) and-cyclobutanecarboxylic acids (2), the stereoisomeric cyclohexyl homologues (3 and4), and di-endo-3-(4-methylbenzoyl)-bi-cyclo-[2.2.1]heptane-2-carboxylic acid (5) with hydrazines yield the cycloalkane-condensed (3(2H)-pyridazinones6–9 and the norbornane di-endo-fused derivatives10. With hydroxylamine, compounds1 and3–5 were transformed to the cycloalkane- and norbornane-condensed 1,2-oxazin-6-ones11–14. Transformation of3–5 led to thetrans-hexahydroanthrone17a and its methylene-bridged analogue24. From the stereoisomeric hexahydro-1(3H)-isobenzofuranones20 and21, the partly saturated anthrones were also prepared; the products (16b and17b) contain the methyl substituent in position 6. On reduction,16b yield the 2-methyloctahydroanthracene22. The structures of the compounds were proved by¹H and¹³C NMR spectroscopy, making use of NOE, DEPT, and CH-COSY techniques.

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Synthese und räumliche Struktur von mit drei- bis sechsgliedrigen gesättigten Homocyclen oder Norbornan kondensierten 3(2H)-Pyridazinonen und 1,2-Oxazin-6-onen

Zusammenfassung Die Reaktion voncis-2-(4-methylbenzoyl)-cyclopropan-(1) und-cyclobutancarbonsäuren (2), der stereoisomeren cyclohexyl-Homologen (3 und4) und von di-endo-3-(4-methylbenzoyl)-bicyclo[2.2.1]heptan-2-carbonsäure (5) mit Hydrazinen ergibt die cycloalkankondensierten 3(2H)-Pyridazinone6–9 und das methylenüberbrückte di-endo-Derivat10. Die Verbindungen1 und3–5 wurden mit Hydroxylamin zu den cycloalkan- und norbornankondensierten 1,2-Oxazin-6-onen11–14 umgesetzt.3–6 reagierten zumtrans-Hexahydroanthron17a und seinem methylenüberbrückten Analogen24. Die teilweise gesättigten Anthrone wurden auch aus den stereoisomeren Hexahydro-1(3H)-isobenzofuranonen20 und21 hergestellt (16b und17b), wobei der Methylsubstituent jedoch in Position 6 lokalisiert ist. Reduktion von16b ergab das 2-Methyloctahydroanthracen22. Die Strukturen der Verbindungen wurden durch NMR-Spektroskopie abgesichert (¹H,¹³C, DEPT, CH-COSY, NOE).

     

Sesquiterpene and iridoids from <Emphasis Type="Italic">Valeriana pseudofficinalis</Emphasis> roots

A new sesquiterpene, named valeriene (1), along with three iridoids, namely valepotriate (2), dihydrovaltrate (3) and acevaltrate (4) were isolated from the ethyl acetate extract of Valeriana pseudofficinalis roots. The structures of these compounds were determined by 1D and 2D NMR, MS techniques, and X-ray single crystal diffractometry. This is the first report of the chemical components isolated from this plant. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 308–310, May–June, 2009.     

Two novel phenolic compounds from <Emphasis Type="Italic">Stenoloma chusanum</Emphasis> and their antifungal activity

Two new phenolic compounds, 4-O-β-D-(6-O-gentisoylglucopyranosyl) vanillic acid (1), 2-O-β-D-(6-O-gentisoylglucopyranosyl) gentisic acid (2), together with three known compounds, vanillic acid (3), syringic acid (4), and gentisic acid (5), were isolated from the whole part of Stenoloma chusanum (L.) Ching. Structures of the two new compounds 1, 2 were elucidated on the basis of spectroscopic methods, including twodimensional NMR techniques and HR ESI-MS analysis. The compounds′ activities against Candida albicans, Cryptococcus neoformans, Trichophyton rubrum, Trichophyton mentagrophytes, Microsporum canis, Epidermophyton floccosum, and Aspergillus niger were determined, and the minimal inhibitory concentrations (MIC) were 25–100 μg/mL. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 161–164, March–April, 2009.     

Chemical constituents isolated from the fungus <Emphasis Type="Italic">Monascus</Emphasis> sp.

Further study of a 95% EtOH extract of red mold rice fermented with the yellow mutant of the fungus Monascus sp. led to the isolation of one new chroman derivative, namely monascuskaochroman (1), together with nine known compounds. The structure of the new compound was determined as 4-(1-hydroxy-1-methyl- ethyl)-chroman-4-carboxylic acid amide. The known compounds were identified as monascin (2), ankaflavin (3), (3R,6R,7E)-(+)-3-hydroxy-4,7-megstigmadien-9-one (4), vanillin (5), syringic acid (6), 3,4,5-trimethoxybenzoic acid (7), trans-methyl p-coumarate (8), ferulic acid (9), and methyl N-methyl anthranylate (10).This is the first report of a naturally occurring chroman skeleton isolated from Monascus species. Compounds 4–10 were isolated from this species for the first time. Their structures were elucidated by 1D and 2D NMR spectroscopy together with HR-ESI-MS analysis, and comparison of the spectroscopic data with those reported for structurally related compounds.     

Einwirkung von Schwefel und Ethylenimin auf höhermolekulare symmetrische Ketone, 4. Mitt

The higher molecular ketones, undecanone-6 (1), tridecanone-7 (2), pentadecanone-8 (3), heptadecanone-9 (4) react with ethylenimine and sulfur to give 2,3-disubstituted 5,6-dihydro-1,4-thiazines (9–12) and 2,2-dialkylated thiazolidines (17–20). The reduction of9–12 with formic acid yields the corresponding thiomorpholines13–16 (70–90% yield).9–12 is also obtained by the reaction of -chloro ketones (5–8) and the sodium salt of cysteamine 30–75% yield); cysteamine reacts with1–4 to give the thiazolidines17–20 (37–53% yield).

Teil der DissertationJ. Stalschus, Techn. Hochschule Aachen, 1974.