Über 3,3,6,9,9‐Pentamethyl‐2,10‐diaza‐bicyclo‐[4.4.0]‐1‐decen und einige seiner Derivate. Über synthetische Methoden. 13. Mitteilung

Heinzer, Franz; Soukup, Milan; Eschenmoser, Albert

doi:10.1002/hlca.19780610812

Cited by 64 publications

(11 citation statements)

References 37 publications

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“…3,3,6,9-Pentamethyl-2,10-diazabicyclo[4.4.O]dec-l-ene was synthesized according to the procedure described by Heinzer et al (13) with minor modifications.…”

Section: Methodsmentioning

confidence: 99%

Proton transfer reactions between 4-nitrophenylphenylcyanomethanes and cyclic nitrogen bases in acetonitrile solvent

Dworniczak¹,

Leffek²

1990

Can. J. Chem.

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This paper is dedicated to Projessor Ross Stewart on the occasion of his 65th birthdayMIROSLAW DWORNICZAK and KENNETH T. LEFFEK. Can. J. Chem. 68, 1657 (1990).3,3,6,9,9-Pentamethyl-2,1O-diazabicyclo[4.4.0]dec-l-ene has been synthesized and its proton transfer reactions, together with those of the bases 2,2,6,6-tetramethylpiperidine and 1,2,2,6,6-pentamethylpiperidine, have been studied with the carbon acids 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenylcyanomethane. Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters are reported for the reactions in acetonitrile solvent. Values of the pK, in acetonitrile have been measured for the conjugate acid of each base and the Bronsted (3 value of 0.56 in acetonitrile has been determined for the proton transfer from 4-nitrophenylphenylcyanomethane.

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“…3,3,6,9-Pentamethyl-2,10-diazabicyclo[4.4.O]dec-l-ene was synthesized according to the procedure described by Heinzer et al (13) with minor modifications.…”

Section: Methodsmentioning

confidence: 99%

Proton transfer reactions between 4-nitrophenylphenylcyanomethanes and cyclic nitrogen bases in acetonitrile solvent

Dworniczak¹,

Leffek²

1990

Can. J. Chem.

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“…Die Ausbeuten beziehen sich auf analytisch reines Produkt. Amidins [13] in (1) und (2). An die Verwendung dieses Amidins gebunden sind die Einfachheit des experimentellen Vorgehens sowie die hohen Ausbeuten, nicht aber die Fragmentierbarkeit der Tosyloxycarbonsauren an sich.…”

Section: -Methyl-58-undecadien-ll-olid~* ' Iunclassified

Ein fragmentativer Zugang zu Makroliden: (5‐E, 8‐Z)‐6‐Methyl‐5, 8‐undecadien‐11‐olid

et al. 1979

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“…Inspired by investigations of the Matile group on the importance of polyion‐counter‐ion complexes for cell penetration and remembering the perfect fit between guanidinium groups and so‐called oxy‐anions ( Figure ,a ) that had been used in organic synthesis and in supramolecular chemistry, we had prepared the 1:4 salt 1a ‐4 Fos of octaarginine amide and fosmidomycin to test its in vitro activity against P. falciparum , and we were able to report in 2013 that growth of this parasite (which causes malaria) was much more strongly reduced by the salt than by fosmidomycin itself ( Figure ,b and c ) …”

Section: Introductionmentioning

confidence: 99%

Cell Penetration, Herbicidal Activity, and in‐vivo‐Toxicity of Oligo‐Arginine Derivatives and of Novel Guanidinium‐Rich Compounds Derived from the Biopolymer Cyanophycin

Grogg

Hilvert

Ebert

et al. 2018

Helvetica Chimica Acta

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Oligo-arginines are thoroughly studied cell-penetrating peptides (CPPs, Figures 1 and 2). Previous in-vitro investigations with the octaarginine salt of the phosphonate fosmidomycin (herbicide and anti-malaria drug) have shown a 40-fold parasitaemia inhibition with P. falciparum, compared to fosmidomycin alone (Figure 3). We have now tested this salt, as well as the corresponding phosphinate salt of the herbicide glufosinate, for herbicidal activity with whole plants by spray application, hoping for increased activities, i.e. decreased doses. However, both salts showed low herbicidal activity, indicating poor foliar uptake (Table 1). Another pronounced difference between in-vitro and in-vivo activity was demonstrated with various cell-penetrating octaarginine salts of fosmidomycin: intravenous injection to mice caused exitus of the animals within minutes, even at doses as low as 1.4 μmol/kg (Table 2). The results show that use of CPPs for drug delivery, for instance to cancer cells and tissues, must be considered with due care. The biopolymer cyanophycin is a poly-aspartic acid containing argininylated side chains (Figure 4); its building block is the dipeptide H-βAsp-αArg-OH (H-Adp-OH). To test and compare the biological properties with those of octaarginines we synthesized Adp8-derivatives (Figure 5). Intravenouse injection of H-Adp8-NH2 into the tail vein of mice with doses as high as 45 μmol/kg causes no symptoms whatsoever (Table 3), but H-Adp8-NH2 is not cell penetrating (HEK293 and MCF-7 cells, Figure 6). On the other hand, the fluorescently labeled octamers FAM-(Adp(OMe))8-NH2 and FAM-(Adp(NMe2))8-NH2 with ester and amide groups in the side chains exhibit mediocre to high cell-wall permeability (Figure 6), and are toxic (Table 3). Possible reasons for this behavior are discussed (Figure 7) and corresponding NMR spectra are presented (Figure 8).

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Über 3,3,6,9,9‐Pentamethyl‐2,10‐diaza‐bicyclo‐[4.4.0]‐1‐decen und einige seiner Derivate. Über synthetische Methoden. 13. Mitteilung

Cited by 64 publications

References 37 publications

Proton transfer reactions between 4-nitrophenylphenylcyanomethanes and cyclic nitrogen bases in acetonitrile solvent

Proton transfer reactions between 4-nitrophenylphenylcyanomethanes and cyclic nitrogen bases in acetonitrile solvent

Ein fragmentativer Zugang zu Makroliden: (5‐E, 8‐Z)‐6‐Methyl‐5, 8‐undecadien‐11‐olid

Cell Penetration, Herbicidal Activity, and in‐vivo‐Toxicity of Oligo‐Arginine Derivatives and of Novel Guanidinium‐Rich Compounds Derived from the Biopolymer Cyanophycin

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