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.

Über eine präparativ brauchbare synthese von 2,3-diphenylbutadienen

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.

Synthese der β-hydroxyäthanphosphonsäure

Discontinuous electrokinetic chromatography of parabens using different substituted resonances as pseudostationary phases

Resorcarene derivatives, negatively charged even at moderate pH, were synthesized and employed as pseudostationary phases to achieve mobilities exceeding that of the electroosmotic flow. Under these conditions, a discontinuous electrolyte system was developed which allows the separation of four uncharged homologous 4-hydroxybenzoic esters (parabens) within a zone of resorcarene electrolyte, and the detection of these UV active compounds in a resorcarene-free zone, free from the high UV background absorbance of the resorcarenes. Resorcarenes, with differently charged functionalities (carboxylate and phosphate groups) to provide the electrophoretic mobility and with alkyl residues of differen…

ChemInform Abstract: (o-Hydroxyphenyl)methylphosphonic Acids: Synthesis and Potentiometric Determinations of Their pKa Values.

Bis-ferrocene derivatives of bridged calix[4]arenes: syntheis, X-ray crystal structure and electrochemical properties

The reaction of chlorocarbonylferrocene (2) with bridged calix[4]arene macrocyclic compounds, in which two opposite para-positions are connected by an additional aliphatic chain where n = 5 (1a) or n = 8 (1b) respectively, gave the corresponding new redox-active bis-ferrocene derivatives of bridged calix[4]arenes, 3a and 3b. An X-ray diffraction study of 3a shows that the caliz[4]arene has a cone conformation in which the two ferrocene substituents are located on the phenolic units connected to each other by the aliphatic chain bridge. Cyclic voltammetric and coulometric studies in dichloromethane reveal that 3a and 3b undergo reversible two electron oxidations at + 0.90 V (versus SCE), sug…

The kinetics of the electrophilic bromination of 17 oligonuclear phenolic compounds with molecular bromine in acetic acid were studied at 22°C. Some of these compounds, consisting of up to 6 phenolic units, which are linked in ortho-position by methylene bridges, and having only one (or two) reactive ortho-position(s) at the end of the molecule, were synthesized for the first time. It could be shown, even for hexanuclear compounds, that the variation of substituents at one end of the molecule leads to a change in the reactivity at the other end, that means over a distance of 22 nonconjugated covalent links. So far, this can be explained only by a chain of intramolecular hydrogen bonds betwe…

Regio- and diastereoselective condensation of resorcarenes with primary amines and formaldehyde

Abstract Mannich reactions of resorcarenes 1 with chiral amines yield single diastereomeric tetrakis-(benzodihydro-1,3-oxazine) derivatives 2 in high yields (80–90%). Epimerisation of these products occurs in the presence of acid.

Phosphonomethyl-substituted phenols are readily obtained from o-hydroxymethylated phenols and trialkyl phosphites. The free acids, incorporated into phenol-formaldehyde resins, act as cation exchangers with remarkable selectivity for different metal ions.

(o-Hydroxyphenyl)methylphosphonic Acids: Spectrophotometric determination of their pKavalues and of the deprotonation sequence

UV/VIS Absorption spectra of nitrosubsituted (o-hydroxyphenyl)methylphosphonic acids (o-(phosphonomethyl)phenols) were measured as a function of pH at 25° in 0.1M NaClo4 solutions. Computational treatment of the whole set of optical density data between 200 and 500 nm resulted in the determination of the dissociation constants of these polyacids and also of the individual electronic spectra of all the species involved in the deprotonation sequence. The spectral behavior gives information on the structure of the anions formed and consequently the order of the subsequent deprotonation steps could be deduced. For the (2-hydroxy-3-nitro(or 5-nitro)phenyl)methylphosphonic acid and the 2-hydroxy-…

Double and triple calix[4]arenis connected via the oxygen functions

New macrocyclic molecules are described containing two or three p-tert-butylcalix[4]arene subunits connected via their oxygen atoms. These macrocycles are available by two general methods which are capable of producing assemblies with bridges of varying rigidity and length.

The first dissociation constant of oligonuclear phenolic compounds consisting of one nitrophenol unit besides further alkyl phenol units (10 dinuclear, 15 trinuclear, 6 tetranuclear compounds, and 4 nitrophenols as model) was determined spectroscopically in water/methanol (50/50 by vol.) at 25°C. For the ortho-linked title compounds with the nitrophenol unit at the end of the molecule a decrease of pK1 is observed which becomes stronger with increasing chain length. The introduction of bulky groups in ortho-position of the dissociating phenolic unit, as well as at the opposite end of the molecule causes a further decrease of pK1. The lowest value is found for a p-nitrophenol unit in the mid…

ChemInform Abstract: Asymmetrically Substituted Calix(4)arenes. A Two-Dimensional 1H NMR Study of a Tetraester Derivative in the cone-Conformation.

Polymere ester von säuren des phosphors, 4. Polymerisation des 2-äthoxy-2-oxo-4,5-dihydro-1,3,2-dioxaphosphorins

Die ringoffnende Polymerisation des 2-Athoxy-2-oxo-4,5-dihydro-1,3,2-dioxaphosphorins (1) mit Alkoholaten als Initiatoren, ist durch folgende Merkmale gekennzeichnet: (a) Zur Polymerisation sind Temperaturen von uber 100°C und Reaktionszeiten von vielen Tagen erforderlich. (b) Es stellt sich ein Polymerisations-Depolymerisations-Gleichgewicht ein. Fur 125°C liegt der maximale Umsatz bei der Polymerisation in Substanz bei 70%. (c) Die Polymerisationsenthalpie hat den Wert 0±12,6 kJ mol—1 (0±3 kcal mol—1). (d) Es werden nur Oligomere gebildet. Die Ausbeute an Substanz mit Pn > 5 liegt um 3%. Die Oligomeren mit Pn = 1 bis 5 werden durch Dunnschichtchromatographie getrennt und durch Massenspekt…

Polymere ester von Säuren des phosphors, 5. Ringöffnende polymerisation des 2-phenoxy-1,3,2-dioxaphospholan durch Michaelis-Arbuzov-reaktion

2-Phenoxy-1,3,2-dioxaphospholane (14) was polymerized by benzyl halogenides at temperatures between 120 and 200°C. It was found that the main chain consists predominantly of unexpected ethylene 1,2-ethanediphosphonate units 7; only about 10% of the monomer was incorporated as the expected 2-hydroxyethanephosphonate structure. An insertion mechanism, proposed by Harwood and Patel for the analogous polymerization of 2-phenyl-1,3,2-dioxaphospholane, does not agree with our experimental results. A hypothesis is developed involving a two step addition process, which exclusively occurs at the chain end. Alternating, one monomer molecule is added by a normal Michaelis-Arbuzov-reaction, and then a …

Polymere ester von säuren des Phosphors, 3. Polymerisation des 2-Äthoxy-2-oxo-1,3,2-dioxaphospholans

2-Athoxy-2-oxo-1,3,2-dioxaphospholan (1) wird durch verschiedene Alkoholate sehr schnell und in hoher Ausbeute zu Poly[oxy(athoxyphosphoryl)oxyathylen] (3) polymerisiert. Die Produkte sind hochviskos und farbols. Sie losen sich in Wasser, Alkoholen, Tetrahydrofuran, Dioxan, Methylenchlorid, Chloroform und Dimethylsulfoxid; unloslich sind sie in Ather und in Kohlenwasserstoffen. Polymerisationsgrade bis 83 (M = 12600) wurden gemessen. In wasriger Losung bei Raumtemperatur erfolgte auch nach Tagen kein merklicher hydrolytischer Abbau. Der mutmaslich anionische Polymerisationsmechanismus und mogliche Nebenreaktionen werden kurz diskutiert. 2-Ethoxy-2-oxo-1,3,2-dioxaphospholane (1) is polymeriz…

Selective N-Protection of a Tetraamino Calix[4]arene Tetraether.

Die inhibitor-efficiency von hydrochinon bei autoxydationsreaktionen

Regioselective synthesis of calixcrowns derived from p-tert-butylcalix[5]arene

Abstract Alkylation of p-tert-butylcalix[5]arene with oligoethylene glycol-ditosylates in the presence of CsF affords the 1,3-bridged calix[5]crowns 1a–c in 51 to 72% yield. In the case of hexaethylene glycol the isomeric 1,2-bridged calix[5]crown-7 2c was obtained additionally. The calixcrowns were further modified by alkylation of the remaining hydroxyl groups.

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 par…

Polymer ester von sären des phosphors, 7. Polymerisation des 1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.1]heptans

1-Oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.1]heptane is transformed in situ (prepared from trimethyl phosphite and glycerol) at −78°C in the presence of a trace of water into a crosslinked polymer containing constitutional repeating units with 5- and 6-membered rings. The reaction with reagents containing hydroxyl groups (water, acetic acid, alcohol) leads to the degradation of the network with the formation of soluble fragments with Pn = 35–50. This reactivity and the possibility to obtain other derivatives from the fragments make this polymer a carrier for pharmacologically active polymers with the advantage of decomposing only into the innocuous components phosphoric acid and glycerol.

N-Isopropylacrylamide andN-Isopropylmethacryl-amide: Cloud Points of Mixtures and Copolymers

The cloud point curve of aqueous solutions of poly(N-isopropylacrylamide), poly(N-isopropylmethacrylamide) and their statistical copolymers were determined turbidimetrically. All the Systems demix upon heating at the cloud point temperature and mix reversibly upon cooling. The cloud points are independent of the total concentration of the solutions (dilute range) and of the sample thickness. Mixtures of the homopolymers poly(N-isopropylacrylamide) and poly(N-isopropylmethacrylamide) in water (ternary systems) exhibit two cloud points, which are nearly the same as the cloud points of the two binary systems homopolymer/water. A quantitative correlation was found between the cloud point temper…

Selective derivatisations of resorcarenes - 2. Multiple regioselective ring closure reactions

Abstract The condensation of the C-pentyl resorcarene 1 with long chain aliphatic diamines 3a-d and excess formaldehyde leads under high dilution conditions to tetrabenzoxazine derivatives 4a-d in which pairs of adjacent oxazine rings are connected by an aliphatic chain. Six new rings are formed per resorcarene molecule during this reaction in a regioselective way. For one example (4a) the chiral cleft-like structure with C2 symmetry was proved by single crystal X-ray analysis. Hydrolysis of the oxazine rings gives the secondary amine derivatives 5a,b with C2v symmetry in high yield.

One-step synthesis of resorcarene dimers composed of two tetra-benzoxazine units

Abstract The condensation of resorcarene 1 with ethylenediamine and an excess of formaldehyde gives, under high dilution conditions, in up to 15% yield the octa-benzoxazine dimer 2 in which two molecules of 1 are connected by four bridges. The structure of 2 has been confirmed by 1 H NMR spectra and MALDI-TOF mass spectra and by hydrolysis of the oxazine rings yielding the secondary amine 3 .

(o-Hydroxyphenyl)methylphosphonic acids: Synthesis and potentiometric determinations of their pKaValues

(o-Hydroxyphenyl)methylphosphonic acids are readily obtained from o-(bromomethyl)- or o-(hydroxymethyl)phenols and trialkyl phosphites. Subsequent hydrolysis leads to the corresponding phosphonic acids. For a series of such compounds, the pKa values have been determined by potentiometry. Their dependence on additional substituents in the aromatic ring is discussed in terms of electronic and steric effects.

Calix[4]arenes with alkylidene bridges, synthesis and conformational properties

Abstract Calix[4]arenes with one or two alkylidene bridges were synthesized by “2+2” fragment condensation. As predicted by molecular mechanics calculations aliphatic residues at the bridging carbon atom(s) prefer the equatorial position.

Gemischte Diester von 2,2′-Methylendiphenolen mit Methacryl- und Crotonsäure und ihre Polymeren. 13C NMR-Untersuchungen zur Strukturaufklärung

The structure of mixed diesters of three 2,2′-methylenediphenols with crotonic acid and methacrylic acid was studied by 13C NMR-spectroscopy. The position of the two acyl groups, expected from the synthetic pathway, was unambiguously confirmed by comparison with the corresponding mono- and diesters containing the same acyl group. In the same way, it was shown that the crotonoyl residue is not involved in the radical polymerisation of these esters.

Selective Derivatization of Resorcarenes. 3. C2-Symmetrical and Transcavity Bridged Bis-Benzoxazines Derived from C2v-Symmetrical Tetratosylates

The regioselective condensation of resorcarene tetratosylates 3/4 with formaldehyde and various primary amines readily gives bis-benzoxazines 5/6 in 65−86% yield. The chiral, C2-symmetrical structure of these compounds has been proved by NMR-spectroscopy and single-crystal X-ray analysis. Bis-benzoxazines 5f and 5i assume in the crystalline state a boat conformation in which the two resorcinol rings bearing the oxazine fragments are nearly parallel. The tosylated resorcinol units are horizontally arranged in a propeller-like fashion, and two intramolecular hydrogen bonds are formed between the phenolic hydroxy groups and the oxygens of the neighboring sulfonyl fragments. Molecular mechanics…

ChemInform Abstract: Dissymmetric Calix(4)arenes with C4- and C2-Symmetry. Synthesis, X-Ray Structures, Conformational Fixation, and 1H NMR Spectroscopic Studies.

ChemInform Abstract: Alkanediyl Bridged Calix(4)arenes: Synthesis, Conformational Analysis, and Rotational Barriers.

Phosphonomethyl Substituted Phenols a New Class of Absorbers and Extractants for Metals

Phosphonomethyl substituted phenols are readily obtained from o-hydroxymethylated phenols and trialkyl phosphites. The free acids, incorporated into phenol formaldehyde resins, act as cation exchangers with remarkable selectivity for different metals.

Xenotransplantation of parathyroids in rats using barium-alginate and polyacrylic acid multilayer microcapsules

The integrity and function of encapsulated parathyroid tissue following xenotransplantation is limited by oxygen and nutrition supply and capsule fibrosis. Since some of these factors depend on stability and biocompatibility of the coating material, multilayer microcapsules have been developed. Parathyroid tissue pieces and digested single cells from pigs were encapsulated in barium-alginate and in polyacrylic acid (PAA) multilayer capsules. After 7 days of culture the function of the encapsulated cells were assessed. Subsequently, in a part of the cultured microcapsules the viability was directly assessed whereas the other part was transplanted in dark animal [DA] rats for 30 days. After e…

ChemInform Abstract: Calix(4)arenes with Resorcinol Units Incorporated in 2,6-Position.

Immobilization of enzymes by multilayer microcapsules

A method is described to obtain a new type of microcapsules for immobilization of enzymes or living cells. The wall of these capsules consists of several layers of poly(ethyleneimine) and poly(acrylic acid). The idea is that diverging properties of the whole assembly can be better controlled when the membrane is built up by several consecutive steps, each being optimized with respect to a special property, for example, permeability or mechanical strength. The encapsulation of acidic phosphatase and the cleavage of p-nitrophenyl phosphate was used as a model system. The charged capsules were characterized by their enzymatic activity, as a function of membrane composition (number and sequence…

The acidity of calix[5]arenes and their linear analogues

Abstract Five new calix[5]arenes containing a single p-nitrophenol unit as the most acidic phenolic unit have been synthesised by (3+2) fragment condensation of a trimer with a p-nitrophenol in the middle with various bishydroxymethylated alkanediyl diphenols. Their first acid constant (pKal) has been determined in 2-methoxyethanol/water (9:1) at 22°C by optical titration. The pKal values are distinctly lower (ΔpKa > 2) than for the trimer, while no difference has been found in comparison to structurally analogous calix[4]arenes. Rigidification of the calix[5]arene skeleton by introducing a single alkanediyl bridge opposite to the p-nitrophenol unit has no effect on pKal. All values are in …

ChemInform Abstract: Selective Ipso-Nitration of tert-Butylcalix(4)arene 1,3-Diethers: X- Ray Structure of an Unexpected Side Product.

Darstellung und polymerisation von diestern aus 2,2′-methylendiphenolen und acryl-, methacryl- bzw. Crotonsäure

Several mono- and diesters of four selected 2,2′-methylenediphenols with acrylic, methacrylic, and crotonic acid were synthesized for the first time. Special emphasis was paid to the preparation of diesters with two different acyl groups which could be obtained via the corresponding monoesters. The radical polymerization of these esters with AIBN (mainly in benzene) gave insoluble (crosslinked) products from dimethacrylates and soluble (linear) polymers from mixed diesters with methacrylic and crotonic acid, while the dicrotonates are not reactive.

Über die polymerisation des 2-chlor-2-oxo-1.3.2-dioxaphospholans

Bei der ringoffnenden Polymerisation des 2-Chlor-2-oxo-1.3.2-dioxaphospholans (I) besteht prinzipiell die Moglichkeit zur Bildung zweier verschiedenartiger Polymerer: eines polymeren Saurechlorids, dessen hauptkette eine Polyesterstruktur aufweist (II), oder eines β-Chlorathylesters der Polyphosphorsaure, d.h. eines Polymeren mit rein anorganischer Hauptkette (III). Das Experiment zeigt, das I durch Erhitzen oder schneller und schonender durch verschiedene Katalysatoren (z. B. NaF, AlCl3, N(CH3)4Cl, Tetraphenylphosphoniumsalze, Triphenylphosphin, Triphenylphosphinoxid) in ein Polymers ubergeht, das in der Hauptkette zu mindestens 90% die Struktur III und zu hochstens 10% die Struktur II auf…

Self-Assembled Hydrogen Bonded Dimers of Calix[4]arenes

Self-assembly of suitably functionalized molecules to well defined supramolecular structures has become a topic of current interest. Various molecules have been designed which are able to mimic in part the recognition and self-organisation processes which are found as a general principle in nature.[1]

ChemInform Abstract: A Series of Calix(4)arenes, Having Two Opposite Para Positions Connected by an Aliphatic Chain.

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.

Eine apparatur zur genauen messung sehr kleiner gasumsätze

Es wird eine Apparatur mit folgenden Eigenschaften beschrieben: Der Gasumsatz wird nach einem Kompensationsverfahren volumetrisch bei konstantem Druck gemessen. Die Genauigkeit der Volumenmessung ist besser als ± 0,2 μl Gas. Die Nullage zeigt einen maximalen Gang von 0,2 μl/h. Substratmengen bis 30 ml konnen eingesetzt werden. Die wesentlichen Teile der Apparatur sind ein Kapillarmanometer als „Nullinstrument” fur die Druckmessung und eine Mikrometerschraube, mit deren Hilfe — ahnlich wie bei einer Kolbenburette — der Gasumsatz gemessen wird. An apparatus for volumetric measurement of gas uptake with an accuracy greater than ± 0,2 μl. is described. A maximum deviation from zero of 0,2 μl./h…

Zur jodometrischen Bestimmung der phosphorigen S�ure

Eine Modifizierung und Kombination verschiedener bekannter jodometrischer Methoden erlaubt die bequeme und genaue Bestimmung von phosphoriger Saure auch im Halbmikromasstab. H3PO3 wird in Phosphatpuffer bei pH 7,0–7,5 mit Jod oxydiert. Das uberschussige Jod wird beim gleichen pH-Wert mit Arsenit zurucktitriert. Die Endpunktsanzeige erfolgte voltametrisch oder mit Starke als Indicator. Der absolute Fehler betragt bei den vorgeschlagenen Versuchsbedingungen ±0,2 · 10−6 Mol H3PO3.

Calix[4]arenes with resorcinol units incorporated in 2,6-position

Abstract Calix[4]arenes containing one or two resorcinol units incorporated via their 2,6-positions were prepared by fragment condensation. Due to the cyclic array of intramolecular hydrogen bonds these molecules assume the cone-conformation.

A New Type of Double Calix[4]arenes by Linkage via the Phenolic Hydroxy Groups

Die reaktion des 2-cyanoisopropylhydroperoxides mit alkali

Polymere ester von säuren des phosphors, 6. Ringöffnende polymerisation cyclischer phosphite und phosphonite durch michaelis-arbuzov-reaktion.–Theorie zur struktur der hauptkette

The hypothesis of Harwood and Patel, suggesting for the polymerization of 2-phenyl-1,3,2-dioxaphospholane a type of insertion reaction to explain the formation of ethylenediphosphinic ester structures besides the normal 2-hydroxyethyl(phenyl)phosphonic ester structures is extended to similar monomers and its theoretical consequences are examined. It is shown that in such a system mutual transformations between ω-hydroxyalkyl-P-acid and alkylenedi(P-acid)structures should occur, establishing a dynamic equilibrium and leading to a sort of azeotropic polymer, in which only one unique composition is kinetically stable. Equations relating to different kinetic parameters are deduced.

Crystal and molecular structure of the (1 : 1) clathrate between a calix[4]arene containing onep-nitrophenol unit and toluene

p-(Methyl,tert-butyl, nitro,tert-butyl) calix[4]arene: toluene, C37H41NO6. C7H8,Mr = 687.87, triclinic,\(P\bar 1\),a = 13.668(2),b = 12.187(2),c = 13.231(1) A,α = 106.78(8),β = 77.88(1),γ = 114.00(1)°,V = 1916.8(8) A3,Z = 2,Dx = 1.19 g cm−3,λ (CuKα) = 1.54178 A,μ = 5.90 cm−1,F(000) = 736,T = 293 K, finalR = 0.068 for 6309 observed reflections. This macrocycle, having different substituents at the positionspara to the hydroxyl groups, is the first one of its type to be studied. The general conformation of this calix[4]arene is compared to similar symmetrical ones. Thetert-butyl groups are not disordered as is usual and toluene is retained between the macrocycles. Two calixarene molecules are…

Die spontane autoxydation des n-Butylmethacrylats

Metal ion complexation by tetraester derivatives of bridged calix [4] arenes

A series of bridged calix [4] arenes (5–10 methylene groups in the bridge) were synthesized and transformed into their tetraester derivatives by reaction with ethyl bromoacetate. The stability constants for complexes of the tetraester derivatives with sodium, potassium and silver cations, determined in methanol by spectroscopic or potentiometric techniques, show a drastic decrease (more than 105 for Na +) for the shorter methylene chains. 1H NMR studies demonstrate a conformational rearrangement of the calixarene part to fourfold symmetry to be necessary for the complexation of a cation, which is prevented by the shorter chains. This is further confirmed by the X-ray structure of a tetraest…

Asymmetrically substituted calix[4]arenes; A two-dimensional 1H NMR study of a tetraester derivative in the cone-conformation

Abstract Several new chiral calix[4]arenes with three or four different substituents in the p-position have been prepared by fragment condensation. Standard derivatization procedures always led to the formation of mixtures of various conformational isomers from which the derivative in the cone-conformation could be isolated only by preparative HPLC. For a tetraester derivative it was shown by two-dimensional 1H NMR spectroscopy, that due to the different substituents the cone-conformation is strongly distorted. The sodium complex of this tetraester, however, assumes a regular cone-conformation again.

Kinetik der Bromierung von Phenolen und phenolischen Mehrkernverbindungen, 5. Mitt.

The kinetics of the bromination of six differently substituted 2,6-bis(hydroxybenzyl)phenols having only one reactivepara position at the phenolic unit in the middle of the molecule were studied in acetic acid at 22°C. The reaction rate decreases if intramolecular hydrogen bonds between one or two hydroxy groups of the adjacent phenolic units and the hydroxy group of the reacting unit become possible, and it is especially low, if these hydrogen bonds are directed to the middle by bulky substituents inortho position. This must be explained by a smaller +M-effect of the hydroxy group of the reacting unit. A kinetic isotope effect is observed in deutero acetic acid, where the reaction rate is …

Über die polykondensation von diäthylphosphit mit aliphastischen diolen

Die Umesterungsreaktion von Diathylphosphit mit linearen Diolen HO–(CH2)x–OH (x = 2–6 und 8) wurde untersucht. Ihre Bilanz zeigte, das neben der angestrebten Umesterungsreaktion in teilweise sehr erheblichem Umfang auch Atherstrukturen gebildet werden. Diese bis jetzt in diesem Zusammenhang noch nicht beschriebene Reaktion verlauft sehr wahrscheinlich im Sinn einer direkten Alkylierung der alkoholischen OH-Gruppen durch die Phosphitestergruppen, denn sie erfordert keinen Katalysator. Die Estergruppen gehen dabei in saure P-OH-Gruppen uber, die unter den angewendeten Bedingungen nicht mehr ohne weiteres zur Kondensation mit den Diolen befahigt sind. Das Verhaltnis von unerwunschter Atherbild…

Selektive enzymatische Schutzgruppenabspaltungen: Der n-Heptylester als Carboxylschutzgruppe in der Peptidsynthese

Selective Enzymatic Removal of Protecting Groups: n-Heptyl Esters as Carboxy Protecting Functions in Peptide Synthesis Amino acid heptyl (Hep) esters are accessible as generally crystalline hydro tosylates 3 from the amino acids by azeotropic esterification with 1-heptanol in high yields. They can be condensed with Z-, Boc-, and Aloc-protected amino acids to give the dipeptides 7–9 in the presence of 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ). From the fully protected dipeptides the N-terminal protecting groups are cleaved by chemical methods without affecting the Hep esters. On the other hand, the heptyl esters can be hydrolyzed under mild conditions (pH = 7.0, 37°C) and with hi…

Highly efficient separation of amines by electrokinetic chromatography using resorcarene-octacarboxylic acids as pseudo-stationary phases

Abstract Resorcarene-octacarboxylic acids, macrocyclic molecules built up by four alkylidene-bridged resorcinol units, were synthesized and used as pseudostationary phases in electrokinetic chromatography (EKC). Resorcarenes provide a stable structure and good solubility in electrolytes even with organic modifiers. The high electrophoretic mobility of the resorcarene-octacarboxylic acids introduced here as pseudostationary phases is based on the eight partly deprotonated carboxylic groups. This offers a broad migration time window, which is the main parameter for the resolution of peaks. From three compounds with different alkyl chain lengths (C 1 , C 5 , C 11 ), the C 11 -resorcarene-octa-…

Über eine Reaktion vono-Hydroxybenzylalkoholen mit Estern von Säuren des Phosphors mit der Koordinationszahl 3

Abstract o-Hydroxybenzyl alcohol reacts with trimethyl phosphite under smooth conditions to o-hydroxyphenylmethane phosphonic acid dimethyl ester. This unusual reaction is of widest applicability. Derivatives of o-hydroxybenzyl alcohol independent of type, number or position of substituents in the ring, react with alkyl esters of phosphorous, phosphonous or phosphinous acids in an analogous process, forming the corresponding o-hydroxyphenylmethane phosphonic or phosphinic esters or phosphine oxides.

A calixarene-based chromoionophore for the larger alkali metals

Abstract A bis(arylazo)calix[5]arene crown ether derivative displays large spectral changes upon complexation of cesium and rubidium salts, with good selectivity over the smaller alkali metals.

ChemInform Abstract: A New Route to Chiral Calix(4)arenes via 1,3-Derivatization.

Calix[4]arenes bridged at the lower rim

Calix[41 arenes, in which two opposite p-positions are linked by an aliphatic chain, and their derivatives show transport or complexation properties strongly dependent on the length of this chain. Bicyclo-calix[4]arenes, a special case of 1,3-bridged calix[41 arenes, and annelated calix[41 arenes, a special case of 1 ,&bridged calix [4] arenes, are also described. Although the preferred conformation of calix[4]arenes is the coneconformation due to its stabilization by a cyclic array of hydrogen bonds between the phenolic hydroxyl goups, these molecules are flexible, with a cone to cone inversion rate of about 150 8-1 for a calix[glarene at 47OC (ref. 1). The cone (or any other) conformation…

Die Radikalausbeute beim thermischen Zerfall von Azoisobuttersäuredinitril in Gegenwart von Sauerstoff

Mit Hilfe markierter Azoverbindungen wurde der gekreuzte Abbruch zwischen Primarradikalen gemessen, und zwar in mit Sauerstoff gesattigten Losungen bei 90°C. Fur verschiedene Losungsmittel wurden folgende maximale Werte gefunden (in Mol-% bezogen auf die Menge an zerfallener Azoverbindung): Benzol: 1,2; Toluol: 0,6; n-Propylacetat: 0,4; Dioxan: 0,4; Cyclohexan: < 0,1; Methylmethacrylat: < 0,1. Aus diesen Ergebnissen folgt, das die wirksame Radikalausbeute bei Autoxydationsreaktionen, die durch Azoisobuttersauredinitril gestartet werden, unter den ublichen Reaktionsbedingungen eine konzentrationsunabhangige Grose ist. Aufgrund theoretischer uberlegungen war das nicht von vornherein sicher. W…

Copolymers from styrene and 1-vinylimidazoles (4a–f), form low spin adducts with iron(II) porphyrins and iron(III) porphyrins, when the content of imidazolyl groups in the polymer is ten mole percent or more. With polymers having a content of imidazolyl groups of less then one mole percent, only high spin adducts are observed. With terpolymers, in which the porphyrin is covalently bound to the copolymer the same phenomenon is observed. Only the high spin Fe(II) porphyrin adducts in the solid state adsorb molecular oxygen like cobalt(II) porphyrins under the same conditions. Adsorptions and desorptions of oxygen are much slower in the cases of iron(II) porphyrins than with the cobalt(II) por…

Dissymmetric calix[4]arenes: Optical resolution of some conformationally fixed derivatives

Various possibilities to obtain intrinsically chiral calix[4]arenes are discussed. The enantiomers of three 1,3-dietheresters and one monoether compound derived from dissymmetric calix[4]arenes with C4 symmetry were separated by HPLC using chiral stationary phases and characterized by their CD spectra. © 1993 Wiley-Liss, Inc.

Stereospecific CC-bond formation with rabbit muscle aldolase - A chemoenzymatic synthesis of (+)-exo-brevicomin

Abstract (+)-(1S,5R,7S)-Exo-brevicomin 9, a sex pheromone of the western pine bark beetle, is synthesized using an aldol reaction catalyzed by fructose-1,6-diphosphate aldolase (EC 4.1.2.13) from rabbit muscle as the key step by which the absolute configuration of the target is established.

ChemInform Abstract: New Crown Ether-Like Macrocycles Containing a Nitrophenol Unit. Synthesis and Metal Ion Effects on the Reactivity of Their Acetates in Transacylation Reactions.

ChemInform Abstract: Regioselective Synthesis of Calixcrowns Derived from p-tert-Butylcalix( 5)arene.

ChemInform Abstract: Annelated Calixarenes Composed of Calix(4)arenes with Hydroxy Groups in the Endo and Exo Position.

Effect of media composition on long-term in vitro stability of barium alginate and polyacrylic acid multilayer microcapsules.

For a number of applications stability of microcapsules is a critical factor. Since the maintenance of polyelectrolyte complexes depends considerably on the ion composition we tested the physical properties of barium alginate capsules and searched for conditions to improve stability by a multilayer coating with polyethylenimine (PEI) and polyacrylic acid (PAA). Mechanical stability and diameters were determined in barium alginate capsules and compared with multilayer capsules. Multilayer coating resulted in smaller capsules than barium complexing alone. The difference was more pronounced when CaCl2 was used instead of NaCl during coating. Barium alginate capsules and application of CaCl2 du…

Chemoenzymatische „Chiral-Pool”-Synthese von (+)-exo-Brevicomin aus Kohlenhydraten mit Fructose-1,6-diphosphat-Aldolase

Chemoenzymatic “Chiral-Pool” Synthesis of (+)-exo-Brevicomin from Carbohydrates Using Fructose 1,6-Diphosphate Aldolase Fructose-1,6-diphosphate aldolase (EC 4.1.2.13) catalyzes the stereospecific aldol reaction between 1,3-dihydroxyacetone phosphate (4) and 5-oxohexanal (3) or its 5-dithiane-protected analog 8. The products of the aldol reactions are dephosphorylated with acid phosphatase (EC 3.1.3.2). Whereas the aldol adduct of 3 cyclizes spontaneously to give the bicyclic brevicomin precursor 3, the adduct of 8 first has to be deprotected with sulfuryl chloride and wet silica gel. The resulting bicyclic α-hydroxy ketone 3 is reduced with LiAlH4 to form the 1,2-diol 14 which is then deox…

Mannich Reactions with Amino Alcohols

The condensation of resorcarenes 1 with various amino alcohols and an excess of formaldehyde was studied. The tetrabenzoxazines 2a−e were found as the only products in the reaction with 6-aminohexan-1-ol, 4-aminobutan-1-ol, and 2-aminoethanol, while 3-aminopropan-1-ol forms the tetraoxazine 3 as the main product. In the case of aminoethanols substituted at the 2-position with alkyl groups, the tetraoxazolidines 4 are the preferred reaction products, while 1-methyl aminoethanol (1-amino-propan-2-ol) yields predominantly the tetrabenzoxazine 2f. The structures of all these compounds have been confirmed by NMR spectroscopy and additionally by single-crystal X-ray analysis in the case of 2a and…

ChemInform Abstract: Dissymmetric Calix(4)arenes with C2 and C4 Symmetry.

Synthese de tetrahydroxy-octamethyl [1 4 ] Metacyclophane a partir de 3,4-dimethylphenol. Le tetrahydroxy-octamethyl [1 4 ] Metacyclophane reagit avec le bromoacetate d'ethyle pour donner tetrakis [(ethoxycarbonyl) methoxy]-octamethyl [1 4 ] Metacyclophane qui est analyse par diffraction RX

Kinetische Untersuchungen zur Bildung der E ‐ und Z ‐Enole bei der Thermolyse von 2‐Diazo‐1,3‐dimesityl‐1,3‐propandion in Nucleophilen

Bei der Thermolyse der Diazoverbindung 1 in Ethanol bzw. Piperidin oder Morpholin entstehen die Enole 3a–c von β-Ketocarbonsaurederivaten. Z- und E-Konfigurationen stehen miteinander im Gleichgewicht. Die Bestimmung der Geschwindigkeits-konstanten zeigt, das sich zunachst bevorzugt die Z-Formen bilden; im Gleichgewicht dominieren jedoch schlieslich in den Thermolysemedien die E-Isomeren. In aprotischen, apolaren oder masig polaren Medien uberwiegen dagegen die Z-Isomeren mit einer intramolekularen Wasserstoffbrucke. Investigation on the Kinetics of the Formation of E- and Z-Enols in the Thermolysis of 2-Diazo-1,3-propanedione in Nucleophiles Thermolysis of the diazo compound 1 in ethanol an…

13C nuclear magnetic resonance study of some phosphinolipids: Assignments and conformational studies

13C chemical shifts and 31P, 13C spin-spin coupling constants are reported for six model phosphinates and eight synthetic phosphinolipids. The complex spectra of the synthetic phosphinolipids could be assigned from increments and couplings derived from the model compounds. Based on these investigations the 3J(PC) couplings of 7–15 Hz indicate a preferential trans orientation of the respective head-group carbon relative to the phosphorus. This behaviour is similar to that of natural phosphatidylcholine lipids.

Diastereoselective Functionalization of a Spherand‐Type Calixarene

Condensation of 5,5'-di-tert-butyl-2,2'-dihydroxybiphenyl (1) with formaldehyde yields a cyclic trimer 2 (and tetramer 3) having three (four) methylene groups less than a calix[6]arene (calix[8]arene). Alkylation of the (flexible) trimer with ethyl bromoacetate gives exclusively the stereoisomer 4 with C 2 symmetry, while the isomer with D 3 symmetry is not observed. Two isomers 6a and 6b (C 2 and C 1 symmetry) are obtained by treatment with tert-butyl bromoacetate which both are converted by transesterification with methanol into the same hexamethyl ester 5 having C 2 symmetry. These results are rationalized by restricted rotation around Ar-Ar bonds for larger O-alkyl groups also around Ar…

The synthesis of double-calixarenes

Abstract Macrocyclic molecules consisting of two calix[4]arene moieties linked via their p-positions by one 1, two 2 or four 3 aliphatic chains were synthetized for the first time.

ChemInform Abstract: Calix(4)arenes (I) with Alkylidene Bridges: Synthesis and Conformational Properties.

Nachweis des di-2-cyanoisopropylperoxides bei der zersetzung von azoisobuttersäuredinitril in gegenwart von sauerstoff

Das Di-2-cyanoisopropylperoxid entsteht in etwa 5-proz. Ausbeute bei der Zersetzung von Azoisobuttersaredinitril unter Sauerstoff in Isobutyronitril als Losungsmittel. Thermisch zerfallt das Peroxid est oberhalb von 120°C mit mesbarer Geschwindigkeit in einer Reaktion erster Ordnung. Die Aktivierungsenergie, in Cumol als Losungsmittel, wurde zu 37,9 kcal · mol−1 bestimmt. Werte fur die Zerfallskonstante bei 140°C sind in Cumol 0,057 h−1, in tert-Butylbenzol 0,073 h−1, in Chlorbenzol 0,18 h−1 und in o-Dichlorbenzol 0,23 h−1. Di-2-cyanoisopropylperoxide is formed when azobisisobutyronitrile is decomposed under oxygen in isobutyronitrile as a solvent. The yield amounts to ca. 5%. Thermal decom…

Selective Derivatizations of Resorcarenes. 4. General Methods for the Synthesis of C2v-Symmetrical Derivatives