Recent developments in the chemistry of adamantane and related polycyclic hydrocarbons

Bingham, Richard C.; Schleyer, Paul von Ragué

doi:10.1007/bfb0051406

Cited by 27 publications

(6 citation statements)

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“…As may be seen from Fig. 2 representing the record by a differential refractometer of a separated mixture of adamantane and four methylated adamantanes 6,11,15 and 17, gel chromatography enables the separation of this mixture with an efficiency which is comparable with the efficiency of a gas chromatography. The peak resolution (r) of a gel column, calculated according to the relationship employed in gas chromatographl7, is listed for neighbouring pairs of components in Fig.…”

Section: Resultsmentioning

confidence: 90%

“…In an earlier paper 14 1 Methyladamantanes (6,11,15,17), ethylmethyladamantanes (8,13,16,18), • adamantane, ~ I ,3-diethyladamantane. Separation of a Mixture of Methylated Adamantanes on a Gel Column 1 Tetramethyladamantane (17), 2 trimethyladamantane (15), 3 dimethyladamantane (11), 4 methyladamantane (6), 5 adamantane. graphy of alkyladamantanes the differences of the elution indexes on a polar or non--polar phase may be calculated on the basis of alkyl increments using a similar relationship.…”

Section: Resultsmentioning

confidence: 98%

“…), 1-ethyladamantane (201 ml), 1-isopropyladamantane (197 ml), in comparison with the sequence 1-methyladamantane (202 ml), 1,3"dimethyladamantane (194 ml), 1,3,5-trimethyladamantane (186 ml). In adamantanes with cyclic substituents, as for example 1-phenyladamantane or 1-(2' -butyl)adamanta ne c14H24 193 0·78 13 1-ethyl-3-methyladamantane Cl3H22 192 0·77 14 1 ,3-diethyladamantane c14H24 189 0·74 15 1 ,3,5-trimethyladamantane c13H22 186 0·72 16 1-ethyl-3,5-dimethyladamantane C14H24 184 0·70 17 1 ,3,5, 7 -tetramethyladamantane c14H24 178 0·65 18 1-ethyl-3,5, 7 -trimethyladamantane C1sH26 176 0·63 19 3,3-diethyl-5,5' -dimethyl 1,1'-diadamantyl, these bulky substituents cause practically the same decrease in the elution volume as methyl or ethyl. The increase of the ring in the adamantane structure, or the condensation of another ring to it (as in hydrocarbon 4) has a still weaker effect than the methyl group.…”

Section: Resultsmentioning

confidence: 99%

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Gel chromatography of adamantane hydrocarbons

Hála¹,

Pecka²,

Kremanová³

1974

Collect. Czech. Chem. Commun.

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Elution volumes of thirty polycycloalkanes with adamantane and other structures were determined for gell chromatography on styrene-divinylbenzene gel in tetrahydrofuran. Elution volumes of methyl ethyladamantanes substituted on bridge heads can be determined on the basis of alkyl increments. In the series of polycycloalkanes of various structures a linear relationship between the distribution constants and effective molecular diameters has been established. A linear correlation has also been found between the elution volumes of isomeric tricycloalkanes and their relative enthalpies calculated from conformational analysis.Polycycloalkanes which constitute a considerable proportion of heavy mineral oil fractions are still little investigated because in consequence of the high number of existing isomers they represent the most complex structural class of hydrocarbons . occurring in petroleum. For the separation of complex hydrocarbon fractions of this type methods are advantageous that permit the separation of the mixtures on the basis of the size or the shape of the molecule. In our preceding papers 1 -3 in which we studied the methods of analysis of polycycloalkanes with adamantane structure we found two methods, viz. extractive crystallization with thiocarbamide 4 and thermodiffusion 5 , as suitable for the isolation of adamantane hydrocarbons from petroleum. In this paper we tested on model substances the method of gel chromatography for the separation of adamantan~ hydrocarbons.Gel chromatography was used originally predominantly for the separation of polymers and other macromolecules. Today, when gels with low exclusion limit are available gel chromatography may also be employed for the separation of smaller molecules. In the separation of hydrocarbon mixtures the elution of components is directed by the effective molecular volume exclusiveJy6. The following factors are mentioned in literature as having a bearing on the effective volume of molecules and which are in correlation with the elution volumes of hydrocarbons: the length of the hydrocarbon chain 7 • 8 , molar volume 9 • 1 0 , molecular mass 11 and various dimensions of molecular models 12 . Schulz 13 found in isoalkanes a relationship between the molar volume and the average number of synclinal (gauche) butane interactions in the molecule, which enables the computation of the elution data from the structure and the conformation. The majority of the relationships mentioned was inferred from the elution volumes of alkanes and aromatic hydrocarbons. No detailed data are available on gel chromatography of saturated polycyclic hydrocarbons.

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

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Gel chromatography of adamantane hydrocarbons

Hála¹,

Pecka²,

Kremanová³

1974

Collect. Czech. Chem. Commun.

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“…This method allowed the preparation of the radiotracer in ultrapure form in only 25 min, with an overall radiochemical yield up to 75% relative to 99m Tc-pertechnetate starting material. Then, the adamantane-based scaffolds bearing one (44), two (45), or three (46) GPI were labeled with the 99m Tc radiotracer in one chemical step, and no further purification was necessary (Figure 7). The affinity of each negatively charged GPI-containing radiotracer for the surface of living prostate cancer cells was measured.…”

Section: Adamantane Conjugated Peptides As Ligands For Binding Cell Smentioning

confidence: 99%

“…The most common first step to functionalize adamantane backbone is the halogenation in the bridgehead positions using selective C–H activation of the tertiary carbon atoms, which display the most stable carbocations as intermediates . Other various types of synthesis have been also widely reviewed , in particular adamantane rearrangements , the formation of unsaturated derivatives , or the introduction of heterocylic substituents . More recently, diverse poly‐functionalizations of adamantane with different residues in the bridgehead positions have been reported , especially for the preparation of molecular tripods for surface tailoring including self‐assembling monolayers, TiO 2 semiconductor surfaces, and atomic force microscopy gold tip modification.…”

Section: Introductionmentioning

confidence: 99%

Multifunctional adamantane derivatives as new scaffolds for the multipresentation of bioactive peptides

Grillaud

Bianco

2014

Journal of Peptide Science

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The remarkable structural and chemical properties of adamantane afford attractive opportunities to design various adamantane-based scaffolds for biomedical applications. A wide range of mono-functionalized adamantane compounds have already been investigated and reviewed, mostly as anti-viral agents. The four bridgehead positions of adamantane provide many possibilities to design poly-functional derivatives, and the recent conception of adamantane building blocks with multiple substituents has shown promising applications in several domains. In this review, we provide a detailed description of the different ways to synthesize multifunctional derivatives starting from adamantane molecule as the main core. We will then describe the interesting biological activity of the diverse multivalent scaffolds, focusing in particular on peptide-based systems. The results reported here will certainly encourage the development of novel adamantane-based structures for biological purposes.

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Polare Effekte bei organischen Reaktionen

Grob

1976

Angewandte Chemie

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Versuche zur quantitativen Erfassung polarer Substituenteneffekte bei organischen Reaktionen durch ,,induktive Substituentenkonstanten" griinden auf der Annahme, daD diese Effekte von der Art der beobachteten Reaktion unabhangig seien. Wie Messungen der Geschwindigkeitskonstanten von nucleophilen Substitutionsreaktionen zeigen, gilt diese Annahme auch bei gesattigten Molekiilen nur bedingt. Sie versagt, wenn der Substituent ein Elektronendonor, das Reaktionszentrum ein Elektronenacceptor ist und beide iiber a-Bindungen hyperkonjugiert sind. lm Extremfall kann die Polarisierung zu heterolytischer Fragmentierung fuhren. Einf&rungDie iibliche Beschreibung organischer Verbindungen mit Symbolen wie ROH, RCHO oder RCOOH impliziert, daD chemische Veranderungen an den funktionellen Gruppen, hier also an der Hydroxyl-, Formyl-bzw. Carboxylgruppe stattfinden, der Rest des Molekiils sich dagegen nicht beteiligt.

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Recent developments in the chemistry of adamantane and related polycyclic hydrocarbons

Cited by 27 publications

References 254 publications

Gel chromatography of adamantane hydrocarbons

Gel chromatography of adamantane hydrocarbons

Multifunctional adamantane derivatives as new scaffolds for the multipresentation of bioactive peptides

Polare Effekte bei organischen Reaktionen

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