Beiträge zur Chemie der Pyrrolpigmente, 59. Mitt.

By investigation of bilatrienes-abc possessing a rigid tautomeric structure within their pyrromethene fragment, using¹³C-NMR spectroscopy, a criterion for the fixation of tautomerism was deduced: if there is a signal in the otherwise unoccupied shift region between 157 and 170 ppm corresponding to an azomethine fragment, tautomerism is fixed. If there is no signal in this region there is a rapidly equilibrating system of the two possible tautomers. This criterion may be used as well for natural substitution patterns. Moreover, assignment of the¹³C-signals by correlation with the easily assigned¹H-NMR signals establishes the position of the fixed tautomeric system. The criterion is applied as well to the 2,3-dihydrobilatrienes-abc where it is in accord with the results gained from a coupling criterion reported earlier.

     

Aromatische Spirane, 22. Mitt.: Darstellung von Cyclopenteno-4,5-indan-1-on und 2-Carboxymethyl-bzw. 4-Chlormethyl-indan als Synthone für Synthesen von anellierten 2,2′-Spirobiindanonen

Summary The title compounds were prepared as follows:tert.-butyl-indane (10) was formylated to give a 72:28 mixture of the aldehydes23a and23b which were submitted to aKnoevenagel-Doebner condensation to afford the cinnamonic acids24. From the mixture, the pure stereoisomer24a was obtained by one crystallization in 57% yield. Its methylester27a could be quantitatively dealkylated to the methylester8 by treatment with AlCl₃ in toluene. Cyclization to the indanone9 was then performedvia the propionic acid7 with polyphosphoric acid in 95% yield. From9 the carboxymethyl derivative30 was obtained by treatment with dimethylcarbonate and NaH. The second synthone 4-chlormethyl-indane (19) was prepared from the corresponding alcohol18 (in 82% yield) which in turn could be obtained from methylester17 by reduction with LiAlH₄. The latter was accessible in 75% yield by dealkylation of ester13.

Herrn Prof. Dr.K. Kratzl mit besten Wünschen zum 80. Geburtstag gewidmet     

Aromatische Spirane, 20. Mitt.: Darstellung von dimethylsubstituierten 2-Carboxymethyl-indan-1-onen und Benzylchloriden als Synthone für Synthesen von di- bis tetramethylierten 2,2′-Spirobiindandionen

Summary The isomeric dimethyl methylbenzoates5, obtained from the bromidesvia Grignard reactions with dimethylcarbonate, were reduced with LiAlH₄ to the hydroxymethyl derivatives6. The latter were then transformed both to the benzylchlorides7 (with SOCl₂) and to the aldehydes8 (with pyridinium chlorochromate).Knoevenagel-Doebner reaction of8 afforded the acrylic acids9 which (after hydrogenation to11) were cyclized to the desired indanones12 with polyphosphoric acid. On the other hand,12c and12e were prepared from dimethyl 3-chloropropiophenone (14) by warming with sulfuric acid. After NaH-catalyzed reaction with dimethylcarbonate, the indanones12 gave the ketoesters15 which then could be hydrogenated to the indanes16. All reactions proceeded with satisfactory to excellent yields (60–90%).

     

Aromatische Spirane, 21. Mitt: Darstellung von Methylphthalaldehydsäuren und ihren Ethylund Methylestern als Synthone für Synthesen von methylierten 2,2′-Spirobiindandionen

Summary The isomeric methyl phthalaldehydic acids11 were obtained from phthalides4 by bromation (NBS) to the 3-bromo derivatives7 and subsequent hydrolysis with water.4 in turn were accessible from dimethyl methyl benzoates1 by dibromination withNBS and subsequent thermical cyclization to the bromo derivatives3 which, on catalytic dehalogenation, afforded the phthalides4. Reaction of11 with methanol or ethanol gave the pseudo-esters13 and14, resp. Short treatment of11 with diazomethane on the other hand yielded the methyl formyl benzoates15b to15e. Prolonged reaction (several hours) gave the oxiranyl compounds17; in addition, the acetonyl derivatives18 were also found, obviously formed by a double methylene insertion into15. All reactions proceeded with good to excellent yields.

     

Synthese und Reaktionen von 2-Arylhydrazono-2-cyan-N,N-dialkyl-acetamidinen

Summary The title compounds3 were synthesized by reaction of arlyhydrazono-malononitriles1 with secondary amines and used for subsequent cyclization reactions. Thus,3 undergoes cyclooxidation by treatment with CuSO₄/pyridine to form the 5-dialkylamino-2-aryl-1,2,3-triazolo-4-carbonitriles4. From4 a and hydrazine hydrate/DMF the 4-(1,3,4-triazolyl-5)-1,2,3-triazole5 c is obtainable. The chloroacetylation of3 is accompanied by hydrolysis of the amino group to yield the arylhydrazono-N-chloracetyl cyanoacetamides6. The quaternisation of6 with pyridins is followed by the Thorpe cyclization to form the 4-amino-5-arylazo-6-hydroxy-3-pyridinio-pyrid-2-on-chlorides8, useful as cationic dyes. The reaction of3 with trichloroacetonitriles yields the 5-arylazo-4-imino-2-trichlormethyl-1,4-dihydropyrimidines10 a–c which can be converted into the 5-arylazo-2-hydrazino-pyrimidine derivatives10 d–f.From10 d the 6-phenylazo-triazolo[4,3-a]pyrimidine derivative11 is obtainable. From3 and phenylisothiocyanate the 5-arylazo-4-imino-1,4-dihydropyrimidin-2-thiones12 arise. The structures were investigated by¹³C-NMR-spectroscopy.

Herrn Prof. Dr. Fritz Sauter zum 60. Geburtstag gewidmet     

Beiträge zur Chemie der Pyrrolpigmente, 32. Mitt.: Zum diagnostischen Wert der13C-Kernresonaz-spektroskopie bei diastereomeren Bilatrienen-abc

All¹³C-NMR signals of (Z, Z, Z)-Aetiobiliverdin-IV- could be assigned to the corresponding positions of the molecular framework using double resonance experiments. In the (Z, Z, E)-isomer the methine carbon signals of the terminal moieties are shifted in a dramatically different manner. Thus they represent an ideal tool for labelling experiments aiming at an experimental support of the photoisomerization hypothesis of the photoreaction of phytochrome.

     

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.     

Beiträge zur Chemie der Pyrrolpigmente, 79. Mitt. Zum strukturellen Einfluß stark raumerfüllender Reste bei 10-substituierten 1,19-Bilindionen

Summary 1,19-Bilindiones bearing a phenanthryl, mesityl,tert-butyl, and isopropyl substituent at the C-10 position were synthesized. Conformational analysis using¹³C- and¹H-NMR spectroscopic techniques and absorption spectroscopy together with semiempirical calculations revealed that the aryl derivatives adopt the common circular helical geometry, whereas thetert-butyl derivative is heavily distorted. The mean planes of the two dipyrrinone moieties are orthogonally positioned to each other. The 10-isopropyl-bilindione tautomerizes to the 10-isopropyliden-biladiene-ac.

     

Dicyanmethylenpyrazolinone und deren Bedeutung als Chromophor. Synthesen mit Nitrilen, 80. Mitt.

1-Phenyl-2-pyrazolin-5-ones1 a–e react with tetracyanoethylene forming the corresponding dicyanomethylenepyrazolin-5-ones2 a–e. The products are deeply coloured with absorption bands between 550 and 650 nm, but low -values and negative solvatochromic effect. By amine-HCN exchange reaction with anilines the red-coloured phenylamino-cyanomethylene-pyrazolinones3–6 are obtained.¹⁵N- and¹³C-NMR-data of2 and quantum-chemical calculations (INDO/S-CI) reveal the extreme polarization and chromophoric properties of the described dicyanomethylene-pyrazolinones.

     

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.     

Beiträge zur Chemie der Pyrrolpigmente, 31. Mitt.: Die Spin-Gitter-Relaxation in den1H-NMR-Spektren von Bilatrienen-abc

The¹H-NMR spin lattice relaxation times of aetiobiliverdin-IV- and biliverdindimethylester were determined using the inversion recovery technique. The relaxation times of protons attached to the terminal rings A and D are longer than those situated at the rings B and C which points to a higher mobility of rings A and D. Moreover these measurements allowed an independent assignment of the¹H-NMR-signals of the methyl groups of biliverdindimethylester.

30. Mitt.:H. Falk undT. Schlederer, Ann. Chem., im Druck.     

Optisch aktive,aromatische Spirane, 11. Mitt.: Synthese optisch aktiver mono- bis heptasubstituierter 5-Methyl- und 5-Ethyl-2,2′-spirobiindane und analoger Naphthalinderivate bekannter Chiralität und enantiomerer Reinheit

Starting from optically active 5,5-dimethyl, diethyl, and 5-ethyl-5-methyl-2,2-spirobiindane as well as from 5-ethyl-spirobiindane-5-carboxylic ester of known enantiomeric purity and configuration 75 mono to polysubstituted 2,2-spirobiindanes have been prepared. Amongst these are several compounds with rings anellated in the 6,7 (and 6, 7) positions, especially a spirohydrocarbon4 x with orthogonal naphthalene units the circular dichroism of which is reported and discussed.Several mono and disubstituted 5-methyl and ethylindanes (1,2) have been prepared as models for synthetic transformations in the spirobiindane series.From the molar rotations of symmetrically diacylated 5,5-dimethyl and diethyl spirobiindanes (4a, 7b, 7c) empirical ligand parameters for acetyl and methoxycarbonyl were determined which gave much better results in the calculation of the rotations of appropriate spirobiindanes (with the shortened polynomal Ansatz) than the -values deduced previously from 5,5-disubstituted spirobiindanes. The significance of these results is briefly discussed.

10. Mitt.:Neudeck, H., Schlögl, K., Angew. Chem.92, 318 (1980), Intern. Ed. Engl.19, 308 (1980).     

Studien zur Chemie von thienoanellierten O,N- und S,N-haltigen Heterocyclen, 10. Mitt.: Synthese von 2- substituierten Thieno-Diltiazemderivaten

Summary The syntheses of 2-acetyl-, 2-benzyl-, and 2-ethyl-thieno-diltiazem derivatives are described starting from the corresponding 5-substituted 3-nitro-2-thiophenthiolvia reaction with racemic methyltrans-3-(4-methoxyphenyl)-glycidate under different conditions (solvent, catalyst, temperature) to obtain purethreo orerythro products. The nitro groups of these products were reduced and the resulting amino esters cyclized. The thieno[2,3-b][1,4]thiazepin-5(4H)-ones were N-alkylated and acetylated in position 3. The desired 2-substituted 4-(2-dimethylaminoethyl)-4,5,6,7-tetrahydro-7-(4-methoxyphenyl)-5-oxothieno[2,3-b][1,4]thiazepin-6-yl acetates were isolated in good yields.

     

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).     

Neuartige synthetische Aspekte der Phosphonat-Phosphat-Umlagerung, 2. Mitt.: Synthese von Enolphosphaten aus 1-Oxoalkanphosphonaten und Schwefelyliden

Acylphosphonates1 react with Sulfur-ylides2 to give enolphosphates3 and phosphonophosphates4. The product ratio of3 and4 is determined by the substituentR ³. IfR ³ is not electronwithdrawing the phosphonophosphate4 is the sole reaction product.

Zählt als 48. Mitt. in der Reihe Reaktionen mit Phosphororganischen Verbindungen; 47. MittF. Hammerschmidt, E. Schneyder undE. Zbiral, Chem. Ber. 1980 im Druck.     

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.     

13C-NMR-Untersuchungen von Substituenteneffekten in mehrfach substituierten Benzen-und Naphthalenverbindungen: Inkrementberechnungen der13C-chemischen Verschiebungen

Summary The aryl¹³C chemical shifts of Cl-substituted 4-amino-, 4-diazonium-N,N-dimethylanilines, N,N-dimethylanilines and differently substituted naphthalenes were assigned by means of different NMR methods. The assignments were compared with chemical shifts obtained by using empirical additivity relationship for mono substituted aromatic substances. As a means of substitutent interactions, the chemical shift difference between calculated and experimental values ( _c ⁱ ) has been used. In the presence of remarkable steric and electronic substituent interactions, large deviations from additivity ( _c ⁱ values up to 15.4 ppm) were found. Which originate primarily from steric interactions between the substitutents. In order to account therefore, correction increments have been developed by employing the _c ⁱ values obtained from 1,2-disubstituted benzenes or naphthalenes. The¹³C chemical shifts of more than seventy substituted benzenes and naphthalenes have been predicted. The results corroborate that reasonable calculation of chemical shifts in sterically hindered benzenes is possible by using the extended additivity rule. The _c ⁱ values are much lower and allow reasonable structural assignments.For external users of this incremental system, a computer program for IBM compatible PC/AT was developed. By means of this program, the¹³C chemical shifts for different benzenes and naphthalenes with or without 1,2-disubstituted correction increments will be calculated and the corresponding spectrum displayed. The program can assist the successful assignment of experimental¹³C chemical shifts.

     

Decorating nickel phthalocyanine periphery by aryl-1,3,4-oxadiazole pendants: synthesis,characterization, and conductivity studies

We have decorated nickel phthalocyanine (NiPc) periphery by four different aryl-[1,3,4]-oxadiazole pendants. Introduction of aryl-[1,3,4]-oxadiazole pendants into the NiPc core results in improved thermal stability, fine-tuning of the position of the Q-band with decrease in band gap, indicating effective electronic communication between the two different ring systems with NiPc core. The magnitude of DC electrical conductivity for aryl-[1,3,4]-oxadiazole-substituted NiPcs 3a–3d is found to be ～10⁵ times higher than the parent NiPc (1). The temperature-dependent DC conductivity studies reveal semiconducting nature of the newly synthesized NiPc compounds with significant decrease in thermal activation energy (ΔE) compared to parent NiPc.     

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.     

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.