Erich F. Paulus

Hydrogen-bonded dimers of tetraurea calix[4]arenes: unambiguous proof by single crystal X-ray analysis

Self-assembly of calix[4]arenes substituted by four urea residues at the wider rim leads to hydrogen-bonded dimers; the first single crystal X-ray analysis of such a dimer is reported.

Guest-Controlled Formation of a Hydrogen-Bonded Molecular Capsule.

The dimerization of the self-complementary resorcarene tetraesters is triggered by the entrapment of a tropylium cation in the pi-basic cavity. Eight intermolecular OH small middle dot small middle dot small middle dotOC hydrogen bonds together with host-guest interactions such as charge transfer and C-H small middle dot small middle dot small middle dotpi bonding are responsible for the high stability of this assembly (see picture). Hereby neither the host-guest interaction nor the interaction of two resorcarene molecules through hydrogen bonds is sufficient by itself to form the complex.

Selective derivatisation of resorcarenes: 1. The regioselective formation of tetra-benzoxazine derivatives

Abstract Four 5,6-benzo-1,3-oxazine rings are formed by the condensation of resorcarenes with various aliphatic or aromatic primary amines and formaldehyde. From four possible regioisomers only the C4 symmetrical compound is isolated in yields of up to 90%. Semiempirical calculations confirm its relative stability, which is due to the possible formation of four intramolecular OH…O hydrogen bonds. The regioselectivity of the reaction is further established for two examples by single crystal X-ray analysis. A solvent molecule is included in the extended cavity.

Synthesis and Extraction Behaviour of Calix(4)arenes Partially Substituted at the Wide Rim by Carbamoylmethylphosphine Oxide (CMPO) Functions

Tetraethers of calix[4]arenes fixed in the cone conformation and substituted at their wide rim by one to three CMPO residues and hydrogen atoms or t-butyl moieties in the remaining position(s) were synthesized. Liquid/liquid extraction studies of selected lanthanides and actinides were undertaken with these calix[4]arenes, including also a linear trimer, in order to obtain a better understanding for the extraction properties of the corresponding calix[4]arene substituted by four CMPO functions. The structure of the 1,3-di-CMPO derivative was confirmed by single crystal X-ray analysis.

Selective derivatisation of resorcarenes: Part 7. The reason for the diastereoselectivity of Mannich reactions with chiral amines

The formation of tetrakis(benzo-3,4-dihydro-1,3-oxazines) 2 by condensation of resorcarenes 1 with various primary amines and an excess of formaldehyde is not only regioselective but, in the case of (R)- or (S)-1-phenylethylamine and their para-substituted (Br, Me) derivatives, also completely diastereoselective. The reaction with the structurally similar (R)-1-aminoindane and (S)-1-(1-naphthyl)ethylamine, on the other hand, produced only a slight excess of one of the two possible epimers 2 and with (R)-1-cyclohexylethylamine no diastereoselectivity was found at all. The presence and the ratio of both diastereomeric structures can be clearly determined by NMR spectroscopy. Inspection of partly converted reaction mixtures suggests that the preferred crystallisation of one of the epimers is responsible for the diastereoselectivity observed in the case of 1-phenylethylamines and not an entirely diastereoselective reaction. The identity of 3, a cyclic triamine obtained as a side product of the Mannich reaction with (R)-1-aminoindane, was established by single crystal X-ray structure analysis.

Selective derivatisation of resorcarenes. Part 5. Acylation of tetrabenzoxazine derivatives

The reaction of the tetrabenzoxazines 2 with acetic anhydride under mild conditions leads selectively and exclusively to the tetraamides 3 in which the oxazine rings are opened; their structure was deduced from their 1H NMR spectra and confirmed for one example by an X-ray single crystal structure analysis; acylation of the hydroxy groups was not observed.

Crown ethers derived from bicyclocalix[4]arenes as chromoionophores

The synthesis of calix[4]arenes in which opposite phenolic units are connected by a poly(oxyethylene) bridge at the narrow rim and a 2,6-dimethylene-4-nitrophenol bridge at the wide rim is reported. For two derivatives with tetra- (4) and penta(oxyethylene) (5) bridges UV-Vis spectrophotometric studies were carried out in buffered solution in the presence of alkali metal ions. Their complexation was associated with changes in their UV-Vis spectra, especially with an increase of the absorption band at 450 nm. For 4 and 5 this was most intense in the presence of potassium and caesium ions, respectively, indicating that the calixarene with the shorter crown ether bridge is selective towards potassium ions and that with the longer bridge towards caesium ions. The X-ray structure analysis of 5 shows a pinched cone conformation for the 1,3-calixcrown part. The p-nitrophenol unit is parallel to one of the unbridged tert-butyl phenol units. Its hydroxyl group points into the cavity, in agreement with comparatively high pKa values. Molecular mechanics was used to model the geometry of the potassium and caesium complexes.

A resorcinol derived calix[5]arene with C5-symmetry

Abstract Condensation of 2,4-dihydroxy-3-hydroxymethyl benzophenone (4) in dioxane/H2SO4 gave the cyclic pentamer 5, a calix[5]arene with regular incorporation of the resorcinol units via their 2- and 6-positions. The structure follows from the 1H NMR and mass spectra and was further confirmed by single crystal X-ray analysis. Dynamic NMR in C2D2Cl4 gave a surprisingly high barrier of ΔG‡ = 17.3 kcal/mol for the cone-to-cone ring inversion.

Reversible Dimerization of Tetraureas Derived from Calix[4]Arenes

Calix[4]arene derivatives, substituted at the wider rim by four urea functions are easily available in great variety. In apolar solvents like benzene or chloroform they dimerize via NH…O=C hydrogen bonds encapsulating a single solvent molecule as guest. The exclusive formation of dimers has been proved in solution by NMR, while their shape has been characterized by single crystal X-ray analysis. The kinetic stability and the rate of the guest exchange have been studied by NOESY experiments using a derivative with lower symmetry.

Head-to-tail connected double calix[4]arenes

SummaryNew macrotricyclic compounds consisting of two calix[4]arene substructures connected by aliphatic chains of various length (three to five carbon atoms) between two oppositep-positions and two distal phenolic oxygens have been synthesized. Starting withp-tert-butyl-calix[4]arene, two O-protected phenolic units are attachedvia ether links in 1,3-position by reaction with the corresponding tosylates. After deprotection, the new calix[4]arene is formed by fragment condensation with 2,6-bisbromomethylated 4-alkylphenols. The structure of one example (8c) has been confirmed by single crystal X-ray analysis. Both calixarene parts assume the cone conformation, a molecule of acetonitrile being included in both cavities.ZusammenfassungNeue makrotricyclische Verbindungen, in denen zwei Calix[4]aren-Einheiten durch aliphatische Ketten unterschiedlicher Länge (drei bis fünf C-Atome) zwischen zwei gegenüberliegendenp-Positionen und zwei gegenüberliegenden Phenolsauerstoffen verknüpft sind, wurden hergestellt. Ausgehend vonp-tert-Butyl-calix[4]aren werden zunächst zwei O-geschützte Phenolbausteine in 1,3-Stellung durch Umsetzung mit den entsprechenden Tosylaten etherartig gebunden. Nach Abspaltung der Benzylether-Schutzgruppe wird durch Fragmentkondensation mit 2,6-bisbrommethylierten 4-Alkylphenolen das neue Calix[4]aren gebildet. Für8c wurde die Struktur durch Einkristallröntgenstrukturanalyse bestätigt. Beide Calixarenteile nehmen diecone-Konformation ein, wobei in die beiden Hohlräume je ein Molekül Acetonitril eingeschlossen wird.