Hydrophile Polymergele mit reaktiven Gruppen, 2. Mitt.: Chelatharze auf Basis von Glucose- und Saccharosemethacrylaten

A widely applicable method for the preparation of chelating resins based on glucose- and sucrosemethacrylate-gels is described. Primary aromatic amino groups were bonded to the carrier by esterification with 4-nitrobenzoylchloride and subsequent reduction of the nitro groups with sodium dithionite. Diazotation and coupling with various chelating ligands (8-hydroxyquinoline, dithizone, anthranilic acid, salicylic acid and pyrogallol) afforded chelating resins with capacities of max. 1.7 mmol/g. Sucrosemethacrylate-gels were etherified with 4-nitrobenzylchloride, epichlorohydrin, 4-nitrophenyl glycide ether (IIb), acrylonitrile and 4-nitrophenylacrylamide (IVb). Reaction of the gels with IIb or IVb and subsequent reduction of the nitro groups yielded reactive carriers with ether-linked primary aromatic amino groups. Diazotation and coupling with 8-hydroxyquinoline yielded chelating resins. The capacities of the gels were 0.6–0.7 mmol/g and these resins were extremely stable to changes inpH.

     

Hydrophile Polymergele mit reaktiven Gruppen, 3. Mitt.: Chelatharze mit Formazan-Ankergruppen auf Basis von Saccharosemethacrylaten

The preparation and properties of hydrophilic chelating resins containing formazans as functional groups are described. Sucrosemethacrylat-gels with primary aromatic amino groups were diazotised and coupled with various substituted phenylhydrazones yielding gels with formazans as chelating anchor groups. The capacities of the gels were max. 1,6 mmol/g. The recycle of adsorption and elution was found to be satisfactory for Co²⁺ and Pb²⁺ whereas only 60% of the bonded Hg^2– could be recovered reversibly.

     

Hydrophile Polymergele mit reaktiven Gruppen, 5. Mitt.: Chelatharze mit phosphorhaltigen Ankergruppen auf Basis von Saccharosemethacrylaten

Phosphorus containing chelating resins were synthesized by reaction of sucrosemethacrylate gels with various dialkylester halides of phosphoric acid and thiophosphoric acid. The sorption capacities of the hydrophilic gels were found to be max. 3.7 mmol/g and equilibrium was achieved within 5 minutes. The recycle of adsorption and elution was found to be satisfactory for Zn²⁺ and Cu²⁺ whereas only 50% of the bonded Hg²⁺ could be recovered reversibly.

     

Hydrophile Polymergele mit reaktiven Gruppen, 1. Mitt.: Herstellung und Polymerisation von Glucose- und Saccharosemethacrylaten

The synthesis of new hydrophilic polymer carriers on the basis of glucose-and sucrosemethacrylates is described. The monomer mixtures were prepared by reaction of glucose or sucrose with methacrylic anhydride or methacry-loylchloride in pyridine and by transesterification of sucrose with methylmethacrylate. Mixtures of methacrylic esters of glucosides could be obtained by analogous reaction of glucosides with methylmethacrylate. Radical polymerisation of the resulting mixtures of mono-and polyfunctional methacrylic esters of glucose and sucrose yielded crosslinked hydrophilic gels, swellable in water and polar organic solvents. The degree of crosslinking is determined by the ratio of mono- to polyfunctional esters in the monomer mixture, which depends on the molar ratio of reactants in the starting mixture. These neutral reactive carriers are stable to changes inpH and to biological degradation.

     

Einwirkung von Schwefel und Ethylenimin auf höhermolekulare symmetrische Ketone, 4. Mitt

The higher molecular ketones, undecanone-6 (1), tridecanone-7 (2), pentadecanone-8 (3), heptadecanone-9 (4) react with ethylenimine and sulfur to give 2,3-disubstituted 5,6-dihydro-1,4-thiazines (9–12) and 2,2-dialkylated thiazolidines (17–20). The reduction of9–12 with formic acid yields the corresponding thiomorpholines13–16 (70–90% yield).9–12 is also obtained by the reaction of -chloro ketones (5–8) and the sodium salt of cysteamine 30–75% yield); cysteamine reacts with1–4 to give the thiazolidines17–20 (37–53% yield).

Teil der DissertationJ. Stalschus, Techn. Hochschule Aachen, 1974.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 16. Mitt.

The reaction of trimethylsilylcarbonamides with halogeno-diorganyl-boranes resp. trihalogenoboranes or organodihalogenoboranes gives monomeric resp. dimeric amidoboranes (borylcarbonamides) and derivatives of 4,8-diaza-1,5-dibora-2,6,9-trioxabicyclo[3.3.1]nonadienes. By reaction of the free acylamides with halogenoboranes in most cases the imide halides could be isolated as the only products. By reaction of the hydrochloride of bis(dimethylamino)-hydroxyborane withn-butyl-lithium followed by addition of the imide halides, the corresponding imidoylamines were formed.¹H,¹¹B, and¹⁹F-nmr spectra, mass spectra and characteristic ir group frequencies are reported.

15. Mitt.:W. Maringgele undA. Meller, Z. anorg. allg. Chem., im Druck.     

Neue Synthesemethoden, 4. Mitt.: Milde einphasenoxidation von Sulfiden und Sulfoxiden zu Sulfonen

The mild oxidation of sulfides and sulfoxides to sulfones with benzyltriethylammoniumpermanganate in organic solvents is described.

1Scholz, D., in Vorbereitung.     

Prins-Reaktionen mit Arylaldehyden, 5. Mitt.: Zur Umsetzung mit 2-Buten und mit Cyclohexen

By reaction of 2-[(1RS, 2RS)-2-hydroxy-1-methyl-propyl]-2-phenyl-1,3-dithiane (1 a) withcis-2-butene oxide, subsequent reduction and acetalizationc-4,t-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 a) andt-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 b) were synthesized as model compounds. For the same purpose by aldol reaction of cyclohexanone and reduction (1RS, 2SR)-2[(RS)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (7 a), (1RS, 2RS)-2[(SR)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (8 a), and (1RS, 2RS)-2[(RS)-hydroxy-(4-nitrophenyl)methyl]cyclohexanol (8 b) and by acetalization (2 , 4 , 4 a, 8 a)-2,4-bis(4-methoxyphenyl)hexahydro-4H-1,3-benzodioxin (9 a) and (2 , 4 , 4 a, 8 a)-2,4-bis(4-nitrophenyl)hexahydro-4H-1,3-benzodioxin (10 b) were obtained. FromPrins reactions, starting with 2-butene3 a,c-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 c),r-4,t-5-dimethyl-c-6-phenyl-1,3,2-dioxathiane-2,2-dioxide (4), and (2Z, 4E)-1,5-diphenyl-4-methyl-2,4-pentadien-1-on (5), and starting with cyclohexene (E)-3-(4-methoxybenzylidene)cyclohexenyl-4-methoxyphenyl ketone (11) have been isolated in low yields.

4. Mitt.:Griengl, H., Nowak, P., Mh. Chem.109, 11 (1978).     

Über Reaktionen mit Betain, 13. Mitt.: Darstellung von trihalogenacetyl-methyliden und ihrer Salze aus Betainen

Reaction of the betaine1 and pyridinebetaine8 with trifluoroacetic anhydride yields the salts4a or9a and the yellow ylide5, respectively. In an analogous manner8 reacts with trichloroacetic anhydride to give11a. In a competitive reaction the trifluoroacetates6 and10 are also formed. Pyridinebetaine hydrochloride reacts similarily with trichloroacetic anhydride.

12. Mitt.:Wittmann H., Sobhi D., Petio F. A., Z. Naturf.31 b, 850 (1976).     

Reaktionen mit phosphororganischen Verbindungen, 48. Mitt.

Reaction of the vicinal diols of steroids1, 5, 7, 10, 13, and16 with TPP/DEAD yields both regio-and stereospecifically the oxosteroids2, 6, 8, 11, 14, and15 by displacement of an axial hydrogen and extrusion ofTPPO besides the cholest-4-en-6-ols9 and12 and the cyclic carbonate3. 16, 17-androstandiol16 gives only the cyclic carbonate17. The different structures of the carbohydrates withcis-diol arrangement19 and21 lead exclusively to cyclic carbonates20 and22 in moderate yields. Treatment of1 with TPP/DEAD/HN₃ affords 3-azido-2-hydroxycholestane4 in addition to the above mentioned2.

     

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 22. Mitt.: Die Reaktion von Trimethylsilylcarbonsäureamiden mit Halogen(diorganyl)boranen

Trimethylsilylacetamide and trimethylsilyltrifluoroacetamide react with halogenodiorganylboranes to monomeric or dimeric amidoboranes depending on the organyl substituents. The compounds were characterized analytically and spectroscopically (NMR:¹H,¹⁹F,¹¹B; MS; IR).

21. Mitt.:A. Meller, W. Maringgele, K. Hennemuth undU. Sicker, J. Z. anorg. allg. Chem., im Druck.     

Reaktionen von elektronenreichen Heterocyclen mit Orthocarbonsäure-Derivaten, 4. Mitt. RegioselektiveLewis-Säure-induzierte elektrophile Substitution an Methylindolen mit Orthoameisensäuretriethylester und Trithio-orthoameisensäuretriethylester

The methylindoles3 a–3 c react with ethyl orthoformate1 a or ethyl trithioorthoformate1 b byLewis-acid catalysis regioselectively to bisindolylmethyl-cations4 and to trisindolylmethanes5. In this type of reactions the orthoester electrophiles represent potent acylation equivalents with nearly equal reactivity.

     

Chinazolinone, 2. Mitt.: Synthese und einige Reaktionen von 2-Azidomethyl-3-aryl-4-chinazolinonen

Starting with the chloromethyl compounds7 the new 2-azidomethyl-3-aryl-4-quinazolinones8 a-h were prepared, some of which have been reduced so far to the corresponding amines9 a, b, e, g by H₂S in good yield. As a first example for the capability of the azides8 to undergo 1,3-dipolar cycloaddition the 2-quinazolinmethyl-1,2,3-triazol-4,5-dicarboxylicacid dimethylesters11 b, e, g were prepared by reacting8 with dimethylacetylenedicarboxylate (10).

1. Mitt.:Domanig R., Arch. Pharm., im Druck.     

Komplexe des zweiwertigen Molybdäns,Derivate des Oktahalodimolybdat(II)-Ions, 4. Mitt.: Darstellungen und Kristallstrukturen von zwei neutralen Komplexen mit 4-Methylpyridin

Mo₂Cl₄ Pic ₄·CHCl₃ (A) (Pic=4-methylpyridine) and Mo₂Br₄ Pic ₄ (B) crystallize in the monoclinic space group.A inC2/c (No. 15) witha=15.175 (4),b=10.847 (2),c=19.946 (6) and =104.52 (2)°;D _o=1.71 (2),D _c =1.72 gcm^–3 forZ=4.B inP2_l/n (No. 14) witha=9.270 (3),b=16.614 (5),c=9.305 (3) and =91.96 (5)°;D _o=2.03 (3),D _c =2.05 gcm^–3 forZ=2.Two halogens and 4-methylpyridines of the MoX ₂ Pic ₂ group are in the trans position. Mo–Mo bond lengths are 2.153 96) forA and 2.150 92) forB. Both molecules are situated on the inversion center resulting in the eclipsed configuration of the ligands around the molybdenum pair. The structure ofB has been refined to the conventionalR factors of 0.08 and 0.098. Disorder on the part of 4-methylpyridines and chloroform molecules stopped the refinement ofA at the endR value of 0.175.Mean Mo–X and Mo–N bonding distances are 2.40 (2), 2.25 (5) forA and 2.53 (3), 2.25 (1) forB.

     

Reaktivität der Pyrrolpigmente, 2. Mitt.: Deprotonierung von 3-Pyrrolin-2-onen

Deprotonation of 3,4-dimethyl-3-pyrrolin-2-on (1) int-butyl alcohol/potassiumt-butoxide solutions takes place on the N atom, as shown by¹H/²H exchange andpK _a determinations of1 (pK=17.1), 1,3,4-trimethyl-3-pyrrolin-2-one (pK _a =17.6), and 3,4-dimethyl-5-methoxy-2_H-pyrrole (pK _a =16.7). The SCF-MO approximation MINDO/3 indicates, however, that in the gas phase deprotonation of1 should occur at the C atom.

1.Mitt.:Ribó, J. M., Trull, F., Mh. Chem.110, 201 (1979).     

Stereochemie von Metallocenen, 43. Mitt.: Torsionsisomere Biphenyl-tricarbonylchrom-Komplexe: Darstellung,Konformationsanalyse und Kinetik der Interkonversion

Complexation of methyl 3-nitro-2-(o-tolyl)-benzoate (2, ano-trisubstituted biphenyl) with hexacarbonyl chromium gave the isomeric Cr(CO)₃ complexes3 and4 both existing as two torsional isomersa andb, as seen by nmr. For the main product3 the preferred conformations of the two torsional isomersa andb were deduced by the lanthanide induced shift (LIS) technique. The activation energy for the interconversion process could be determined from kinetic measurements and especially from¹H-nmr coalescence temperature of the methylsignals. The barrier of 91±1.5 kJ/mol (21.7±0.3 kcal/mol) in3 reflects the interaction of theo-H-atom of the benzene ring passing the Cr(CO)₃ moiety of the benchrotrene ring during the interconversion.A partial optical resolution of3 was achieved by asymmetric reduction with a chiral lithium-aluminium hydride yielding (+)-3 with [] _D ²⁰ +30° (benzene) and the levorotatory alcohol (–)-7.

42. Mitt.:K. Schlögl undR. Schölm, Mh. Chem.109, 1227 (1978).     

Beiträge zur Chemie der Pyrrolpigmente, 38. Mitt.: Zur Assoziation von Gallenpigmenten

The long standing problem of solvent dependent absorption spectra of certain bile pigments such as bilirubindimethylester has been solved by measurement of molecular masses by means of vapour pressure osmometry. Using this method and the investigation of the concentration and temperature dependence of the absorption spectra on several model compounds an association equilibrium for pigments of the rubinoid structural type could be confirmed. Moreover the optical properties of the coexisting species and the corresponding equilibrium constants could be deduced by spectroscopic techniques. Verdinoid pigments lacking free carboxylic functions on the other hand tend to be monomeric in solution. A heteroassociated species involving equimolar amounts of a verdinoid and a rubinoid pigment could be verified existing on adsorbents like silicagel.

37. Mitt.:Falk, H., Thirring, K., Tetrahedron, im Druck.     

Zur Umsetzung von 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-onen mit Diazoalkanen, 2. Mitt.

Summary 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-ones2 undergo regio- and stereospecific 1,3-dipolar cycloaddition reactions with diazomethane or diazoethane to yield 3,4,6a,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones3, which slowly isomerize in solution to give the 3,4,8,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones5. The carbon of the diazoalkane dipole is attached to carbon C-8 of the benzoxazinone. The structures of the obtained products were determined by¹H- and¹³C-NMR spectroscopy. An X-ray crystal structure analysis of3 a was carried out at room temperature:C₁₁H₁₅N₃O₃,M _r =237.26, orthorhombic, Pc2₁n,a=9.173 (5),b=9.133 (4),c=13.281 (6),V=1112.6 (9) ų,Z=4,d _x =1.416 g/cm^–3, =0.93 cm^–1,R=4.33%,R _w =3.95% (919 observations, 168 parameters).

Herrn Prof. Dr. W. Fleischhacker zum 60. Geburtstag gewidmet     

Beiträge zur Chemie der Pyrrolpigmente, 39. Mitt.: Ein Kraftfeldmodell zur konformationsanalytischen Untersuchung von Gallenfarbstoffen

A force field model was designed with respect to the special needs of bile pigments. It is parametrized and tested using partial structures of bile pigments as well as an integral pigment; the solution structures of the molecules were previously deduced using independent experimental methods.

38. Mitt::Falk, H., Schlederer, T., Wolshann, P., Mh. Chem.112, 199 (1981).     

Beiträge zur Chemie der Pyrrolpigmente, 26. Mitt.: Zur anaeroben Photochemie von Gallenpigmenten: Die Lumineszenz von Gallenpigment-Partialstruktursystemen und integralen Farbstoffen

The luminescence properties of about twentyfive model compounds representing the three main partial structures of bile pigments (namely pyrromethenes, pyrromethenones and methylenepyrrolylmethylenepyrrolinones) as well as tripyrrines and the geometrical isomers of aetiobiliverdin-IV- are reported. In these compounds there is usually only a very faint or even no fluorescence and phosphorescene as the pathway of deexcitation. Vibrational internal conversion and photoisomerizations at the exocyclic double bonds are the main anaerobic paths of radiationless decay of the excited states.

H. Falk, K. Grubmayr, E. Haslinger, T. Schlederer undK. Thirring, Mh. Chem.109, 1451 (1978).