Die Struktur des Sphaerophysins

Heesing, Albert; Rolf, Eckard

doi:10.1002/cber.19701030223

Cited by 13 publications

(7 citation statements)

References 7 publications

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“…This derivative corresponds to smirnovine, which is an alkaloid that was originally isolated from Smirnovia turkestana Bge., a leguminous shrub from the desert regions of Central Asia (Ryabinin, 1947(Ryabinin, , 1948. The structure of smirnovine was finally established by Heesing and Eckard (1970) via the synthesis of a dihydro derivative of deacetylsmirnovine, that is, dihydrosphaerophysine.…”

Section: Resultsmentioning

confidence: 99%

“…A sample of N-(4-acetamidobutyl)-N-(3-methyl-2butenyl)amine (4) was prepared as described by Heesing and Eckard (1970). All our attempts to convert this secondary amine to a guanidine by its reaction with S-methylisothiourea failed (which may account for the absence of a previous synthesis of smirnovine).…”

Section: Resultsmentioning

confidence: 99%

“…Synthesis of Smirnovine Picrate. To a stirred mixture of 10 mL of saturated aqueous potassium carbonate and 30 mL of dichloromethane was added 0.352 g of the hydrochloride salt of 4 (Heesing and Eckard, 1970) at room temperature. The stirring was continued for 1 h, and the organic layer was then separated and dried (K2CO3), and the solvent was removed under reduced pressure to provide 256 mg (87%) of the free base 4.…”

Section: Introductionmentioning

confidence: 99%

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Isolation and Characterization of Two Guanidines from Galega orientalis Lam. Cv. Gale (Fodder Galega)

Benn

Shustov

Shustova

et al. 1996

J. Agric. Food Chem.

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The vegetative parts of Galega orientalis Lam. cv. Gale, being tested in Canada as a new cold-hardy fodder crop, were found to contain two hemiterpenoid guanidines: the know alkaloid smirnovine, and its previously unknown (Z)-4-hydroxy derivative. The synthesis of smirnovine picrate is also described for the first time. A sample of G. orientalis from Estonia yielded smirnovine in similar concentrations (0.2%). Although these levels are low, more research is required to confirm that the alkaloids in fodder galega do not pose a threat to livestock in Canada. Keywords: Galega orientalis; fodder galega; guanidines; smirnovine; (Z)-4-hydroxysmirnovine

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Isolation and Characterization of Two Guanidines from Galega orientalis Lam. Cv. Gale (Fodder Galega)

Benn

Shustov

Shustova

et al. 1996

J. Agric. Food Chem.

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“…The readily available monoBoc-protected amine 19 12 was used as our starting material rather than the corresponding acetyl derivative as used by Hessing and co-worker. 11 The guanidinylation of amine 20 was successfully carried out in a mixture of 1,4-dioxane/ CH 2 Cl 2 using excess reagent 1 (Scheme 4). The target compound 21 was isolated in 49% yield along with an unexpected side product 22 which presumably was formed by nucleophilic attack of amine 20 at the carbonyl carbon of a Boc group rather than the imine of the guanidinylation reagent.…”

Section: Scheme 2 Schemementioning

confidence: 99%

“…Compound 20 was prepared according to literature procedure 11 in 30% overall yield from amine 19, mp 133-135°C. 1…”

Section: N-(4'-tert-butoxycarbonylaminobutyl)-n-(3-methylbuten-2yl)ammentioning

confidence: 99%

Synthesis of Biologically Important Guanidine-Containing Molecules Using Triflyl-Diurethane Protected Guanidines

Baker¹,

Goodman²

1999

Synthesis

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The guanidine-containing biologically important molecules, guanadrel, guanoxan, guanethidine and smirnovine have been synthesized using the recently developed triflyl-diurethane protected guanidines.Numerous natural and non-natural guanidine-containing compounds have had an significant impact on agricultural and medicinal chemistry. Moreover, many of these novel molecules have shown unprecedented activity ranging from antimicrobial, antiviral, antifungal to neurotoxic making these compounds and their derivatives clear targets for drug design and discovery. 1 With increasing numbers of bioactive molecules containing the guanidine moiety, there is a continuing need for a general and efficient method for their syntheses. We have recently reported the use of N,N'-di-Boc-N"-triflylguanidine (1) and N,N'-di-Cbz-N"-triflylguanidine (2) for the guanidinylation of amines under mild conditions and in high yields. 2 Application of this procedure has now been extended to the facile syntheses of the therapeutic agents, guanadrel (3), 3 guanoxan (4), 4 and guanethidine (5). 5 We have also applied this method to the preparation of the N,N-dialkylated guanidino-alkaloid, smirnovine (6). 6To date, the preparation of compounds 3, 4, and 5 involves either treatment of the appropriate amine with Smethylisothiourea 4-6 or reaction of a tosylate derivative with guanidine. 5 Both methods often require elevated temperatures and extended periods of time in polar solvents, such as H 2 O, methanol, tert-butanol, or DMF for reasons of solubility. The precursor amine 10 of guanadrel (3) was prepared through ketalization of cyclohexanone (7) with diol 8 7 to provide intermediate 9 (Scheme 1). The subsequent removal of the acetyl group of compound 9 using aqueous hydrazine afforded amine 10 in a reasonable overall yield for the two steps. Using either reagent 1 or 2, the guanidinylation step was carried out with a slight excess of amine 10 at room temperature in the presence of Et 3 N. After an aqueous workup, derivatives 11 and 12 were isolated in 95 and 93% yield, respectively. Catalytic hydrogenolysis under parr conditions led to the deprotection of the Cbz groups of compound 11 in quantitative yield to give guanadrel (3) as the free base. Deprotection of the Boc groups of compound 12 was not possible in the presence of the labile ketal (Scheme 1). Scheme 1The precursor amine 13 of guanoxan hydrochloride (15) was prepared following literature procedure. 8 In an analogous process to the guanidinylation of compound 12, excess amine 13 was treated with reagent 1 in the presence of Et 3 N to afford diBoc guanoxan (14) in quantitative yield. After deprotection with SnCl 4 9 followed by crystalDownloaded by: Simon Fraser University Library. Copyrighted material.

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