Synthesis and Structural Studies of Group 2B Transition Metal Complexes with the Bulky Nitrogen Ligand Bis[ N-(2,6-diisopropylphenyl) imino]acenaphthene

Group 2B transition metal complexes of bis[N-(2,6-diisopropylphenyl)imino]acenaphthene (o,o-iPr₂C₆H₃-BIAN), namely, [Hg(o,o-iPr₂C₆H₃-BIAN)Cl₂] (1), [Zn(o,o-iPr₂C₆H₃-BIAN)₂](ClO₄)₂ (2), and [Cd(o,o-iPr₂C₆H₃-BIAN)₂](ClO₄)₂ (3) have been synthesized and characterized. In complexes 2 and 3, IR, NMR, and conductivity measurements confirm the coordination of two (o,o-iPr₂C₆H₃-BIAN) ligands to the metal center with two discrete perchlorate anions. X-Ray crystal structure of 1 indicates a distorted tetrahedral geometry with two nitrogen atoms from (o,o-iPr₂C₆H₃-BIAN) ligand and two chloride atoms coordinating to the Hg(II) center.     

Synthesen in der Pyridazin-Reihe, 31. Mitt.: Über einige neue polycyclische Azolo- und Azinopyridazine

Zusammenfassung Synthesen von verschiedenen neuen polyazaheterocyclischen Systemen, wie 11H-Imidazo[1,22,3]pyridazino[6,1-b]-chinazolin-11-on (3), 11H-s-Triazolo[4,32,3]pyridazino[6,1-b]chinazolin-11-on (4), der Isomeren 4H-Pyrido[2,34,5]-pyridazino[6,1-c]-as-triazin (6) und 4H-Pyrido[3,24,5]-pyridazino[6,1-c]-as-triazin (9), Pyrido[3,24,5]pyridazino[1,6-b]benzimidazol (14) sowie Pyrido[3,24,5]-s-triazolo[4,32,3]pyridazino[1,6-a]benzimidazol (15) werden beschrieben.

---

Syntheses of pyridazines, XXXI: Some new polycyclic azolo and azino-pyridazines

Syntheses of several new polyazaheterocyclic systems are described, i.e. 11H-Imidazo[1,22,3]pyridazino[6,1-b]quinazolin-11-one (3), 11H-s-Triazolo[4,32,3]pyridazino[6,1-b]quinazolin-11-one (4), the isomeric 4H-Pyrido[2,34,5]pyridazino[6,1-c]-as-triazine (6) and 4H-Pyrido[3,24,5]pyridazino[6,1-c]-as-triazine (9), Pyrido[3,24,5]pyridazino[1,6-b]-benzimidazole (14) and Pyrido[3,24,5]-s-triazolo[4,32,3]pyridazino[1,6-a]benzimidazole (15).

---

---

Heterocyclen, 69. Mitt.     

Formation of a Hydroxo-bridged Dinuclear Ru(III)/Ru(III) Complex from <Emphasis Type="Italic">N</Emphasis>-Methylimidazole and [Ru<Emphasis Type="Italic">Cp</Emphasis>(CH<Subscript>3</Subscript>CN)<Subscript>3</Subscript>]<Superscript>+</Superscript>

Summary. The reaction of [RuCp(CH₃CN)₃]PF₆ with 1 equiv of N-Me-imidazole results in the quantitative formation of [RuCp(¹N-N-Me-imidazole)(CH₃CN)₂]PF₆ (1) featuring a ¹N rather than a ¹C bound N-Me-imidazole ligand. According to DFT/B3LYP calculations, ¹N coordination of N-Me-imidazole is preferred over ¹C coordination by 25.5kJ/mol. Upon exposure to air 1 reacts with oxygen and water to afford the novel hydroxo-bridged dinuclear complex of [Ru₂Cp₂(¹N-N-Me-imidazole)₂(-OH)₂](PF₆)₂ (2) featuring a metal-metal single bond. The dimeric nature of 2 was confirmed by a single-crystal X-ray structure analysis.     

Über Heterocyclen, 22. Mitt.: 3,4,6,7-Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dione

Zusammenfassung Tetrahydro-6-brommethyl-2-oxopyrimidin-5-carbonsäureester reagieren mit Ammoniak bzw. Benzylamin zu Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dionen. Mit 2-Aminopyridin (A) bilden sich Tetrahydro-6-(2-pyridylaminomethyl)-2-oxopyrimidin-5-carbonsäureester, Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dione sowie 5-Äthoxycarbony]-2,3,5,6-tetrahydro-2-oxospiro(pyrimidin-4(1H), 2(3H)-1H-imidazo[1,2-a]pyridinium)bromide.

---

Heterocycles XXII: 3.4.6.7-Tetrahydro-5H-pyrrolo [3.4-d]-pyrimidine-2(1H)-5-diones

Tetrahydro-6-bromomethyl-2-oxopyrimidine-5-carboxylates react with ammonia and benzylamine, resp., to give tetrahydro-5H-pyrrolo[3.4-d]pyrimidin-2(1H), 5-diones. With 2-aminopyridine (A) tetrahydro-6-(2-pyridylaminomethyl)-2-oxopyrimidine-5-carboxylates, tetrahydro-5H-pyrrolo[3.4-d]pyrimidine-2(1H). 5-diones as well as 5-ethoxycarbonyl-2.3.5.6-tetrahydro-2-oxospiro(pyrimidin-4(1H)-2(3H)-1H-imidazo[1.2-a]-pyridinium) bromides are formed.

---

---

Herrn Prof. Dr.O. Hromatka zum 65. Geburtstag gewidmet.     

Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

---

Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase

Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH₂Cl₂ (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H₂O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.

---

Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase

Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH₂Cl₂ (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H₂O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.

     

Bis(2,2′-bipyridine)(4,4′-diuntriacontanyl-2,2′-bipyridine)-ruthenium(II) chloride and related hydrophobic complexes

Summary New synthetic routes to 1-triacontanol and 1-bromotriacontane, and the novel ligands 4,4-diuntriacontanyl-2,2-bipy-ridine, 4-untriacontanyl-4'-methyl-2,2'-bipyridine and 4,4-ditricosyl-2,2-bipyridine are reported, as well as the preparation of the novel ruthenium(II) salts, [Ru(bipy)₂(bipy-4-R-4-R)]Cl₂ (bipy = 2,2'-bipyridine; R = R' = C₃₁H₆₃ or C₂₃H₄₇; R = C₃₁H₆₃, R' = Me).     

Demetallation of coordination compounds of nickel with tetradentate ligands based on S-substituted isothiosemicarbazides

The passage of dry gaseous hydrogen chloride through chloroform solutions or acetone suspensions of S-substituted N¹,N⁴-di(salicylidene)isothiosemicarbazidates of nickel (Ni(LRR)) has led to a demetallization reaction with the liberation in the free state of S-substituted N¹,N⁴-di(salicylidene)isothiosemicarbazides with the general formula N₂LRR (where R is H and R is CH₃ (I); R is H and R is C₂H₅ (II); R is H and R is C₃H₇ (III); R is H and R is C₇H₇ (IV); and R is CH₃ and R is CH₃ (V)). The IR spectra of (I-IV) each showed bands characteristic for an aromatic ring and groups in the 1600–1500 cm^–1 region, with a band of the deformation vibrations of an OH group at 1300 cm^–1. The PMR spectra in CDCl₃ each had two singlets at 12.15-11.25 and 9.00-8.36 ppm which were assigned, respectively, to the protons of an OH group and those of a =CH group. A multiplet in the 7.70-6.83 ppm region belonged to the protons of benzene rings. In the region of lower fields there were the signals of the substituents R and R. In the mass spectra of (I-V), the peaks of the molecular ions, and also the characteristic fragments OH, R, SR, and HSR have been detected.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 604–608, September–October, 1985.     

Crystal Structure of Two Dimethyl 1,3-Thiazolidinedicarboxylates Obtained in Thermal [2 + 3]Cycloaddition of an Azomethine Ylide with 2,2,4,4-Tetramethyl-3-Thioxocyclobutanone

The crystal structures of dimethyl 2,2,4,4-tetramethyl-3-oxocyclobutane-1-spiro-5-3,4-diphenyl-(1,3)-thiazolidine-2,2-dicarboxylate, C₂₆H₂₉NO₅S for V, and dimethyl 3,4-diphenyl-5-isopropylidene-(1,3)-thiazolidine-2,2-dicarboxylate, C₂₂H₂₃NO₄S for VI, have been solved. The 1,3-thiazolidine ring of compound V has got twisted conformation, while in compound VI this ring adopts envelope. In both structures short inter- and intramolecular contacts were found, which can be recognized as hydrogen bonds.     

The supramolecular structures and reactivities of some complexes of chiral crown ethers with borane ammonia

Whereas 1 1 crystalline complexes have been isolated between borane ammonia and methyl 4,6-O-benzylidene-2,3-dideoxy--d-galactopyranosido [2,3-b]-1,4,7,10,13,16-hexaoxacyclo-octadecane (1), methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-b] (methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-k]-1,4,7,10,13,16-hexaoxacyclo-octadecane (3), and (1R,2R,7R,24R)-3,5,8,11,14,17,20,23,26,28-decaoxatricyclo-[21.4.0.0^2,7]octacosane (4), the hosts, methyl, 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido[2,3-b] 1,4,7,10,13,16-hexaoxacyclo-octadecane (2) and 1,4 1,4 3,6 3,6-tetra-anhydro-2,2 5,5-bis-O-oxydiethylenedi-d-mannitol (5) have yielded 2 1 (guest:host) crystalline complexes with borane ammonia as guest. X-ray analyses of the supramolecular structures of BH₃NH₃ ·1, (BH₃NH₃)₂ ·2, BH₃NH₃ ·3, BH₃NH₃ ·4, and (BH₃NH₃)₂ ·5 have been carried out and BH₃NH₃ ·1, BH₃NH₃ ·2, and (BH₃NH₃)₂ ·5 have been shown to reduce acetophenone with enantiomeric excesses of 5, 13, and 10% respectively. Supplementary Data relating to this article (atomic coordinates of the hydrogen atoms and thermal parameters) are deposited with the British Library as Supplementary Publication No. SUP 82017 (74 pages).Dedicated to Professor H. M. Powell.     

4,4′-Dipyridyl and 2,2′-dipyridyl complexes of rare-earth perchlorates

4,4-Dipyridyl and 2,2-dipyridyl complexes of rare-earth perchlorates of the formulaLn(4-dipy)₈(ClO₄)₃HClO₄ · 4H₂O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy=4,4-dipyridyl) andLn(2-dipy)₃(ClO₄)₃ · 6H₂O (Ln=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 2-dipy = 2,2-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed.

---

4,4-Dipyridyl- und 2,2-Dipyridylkomplexe von Seltenerdmetallperchloraten

Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypsLn(4-dipy)₈(ClO₄)₃HClO₄ · · 4 H₂O mitLn=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y und 2,2-Dipyridylkomplexe des TypsLn(2-dipy)₃(ClO₄)₃ · 6 H₂O mitLn=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert.

     

Zur Mannich-Reaktion von Dihydro-6-methyl-2(1H)-pyrimidinonen

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone reagieren mit Formaldehyd und sekundären bzw. primären Aminen zu 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinonen bzw. Hexahydro-2(1H)-pyrido[4,3-d]Pyrimidinonen. Mit Succindialdehyd bzw. Glutardialdehyd und primären Aminen entstehen 5,7-Äthanohexahydro-2(1H)-pyrido[4,3-d]pyrimidinone bzw. Tetrahydro-6,8-propano-6H-pyrimido[1,6-c]pyrimidin-1(2H)-one. Die 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinone geben mit Phenolen Tetrahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-one, mit cycl. -Dicarbonylverbindungen Hexahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2,5(3H, 6H)-dione bzw. Tetrahydrospiro(2H,5H-pyrano[3,2-c][1]benzopyran-2,4(1H)-pyrimidin)-2(3H),5-dione bzw. mit Malonestern -(Tetrahydro-4,4-dimethyl-2-oxo-6-pyrimidyl)-äthylmalonester.Zusammenfassung Dihydro-4.4.6-trimethyl-2(1H)-pyrimidinones react with formaldehyde and sec. and prim. amines resp. to 6-dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones and hexahydro-2(1H)-pyrido[4.3-d]pyrimidinones, resp. succindialdehyde and glutaraldehyde with primary amines give 5.7-ethanohexahydro-2(1H)-pyrido[4.3-d]pyrimidinones and tetrahydro6.8-propano-6H-pyrimido[1.6-c]pyrimidin-1(2H)-ones, resp. 6-Dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones react with phenols to tetrahydrospiro([1]benzopyran-2.4(1H)-pyrimidin)-2(3H)-ones, with cyclic -dicarbonyl compounds to hexahydrospiro([1]benzopyran-2.4 (1H)-pyrimidin)-2,5 (3H), 6H)-diones and tetrahydrospiro(2H,5H-pyrano[3.2-c][1]benzopyran-2.4(1H)-pyrimidin)-2(3H),5-diones, resp., with malonates -(tetrahydro-4.4-dimethyl-2-oxopyrimidyl-6)-ethylmalonates.

---

Mannich reaction with dihydro-6-methyl-2(1H)-pyrimidinones

---

Herrn Prof. Dr.F. Kuffner zum 65. Geburtstag gewidmet.     

Darstellung,chiroptische Eigenschaften und absolute Konfiguration von 7.7′-Spiro-bi[3]ferrocenophan-6.6′-dion

Zusammenfassung 7.7-Spiro-bi[3]ferrocenophan-6.6-dion (3) wurde durch Chromatographie an partiell acetylierter Cellulose optisch aktiv erhalten (optische Ausb. um 10%). Die optische Aktivierung gelang auch durch kinetische Racematspaltung des durch Reduktion von3 leicht zugänglichencis,cis-Diols4 a mit (+)--Phenylbuttersäureanhydrid und Rückoxidation zu3 (optische Ausb. etwa 33%). Aus den Ergebnissen konnten die absol. Konfigurationen und optischen Reinheiten für3 und4 a abgeleitet werden: (–)-(7S)-3 bzw. (+)-(6S,6S)-4 a; []_D ^max 1070^o bzw. 115^o. Diese Werte wurden durch Anwendung derNMR-Methode auf den Bis-(O-methylmandelsäureester) von4 a bestätigt. Der Circulardichroismus der beiden Spiroverbindungen im Bereich der Ferrocenbande (um 440 nm) wurde gemessen und wird diskutiert.

---

Optically active, aromatically substituted spiranes, II: Synthesis, chiroptical properties and absolute configuration of 7.7-spiro-bi[3]ferrocenophane-6.6-dion

7.7-Spiro-bi[3]ferrocenophane-6.6-dion (3) was partially resolved by chromatography on partially acetylated cellulose (optical yield appr. 10%). Optical resolution was also achieved (with optical yields of appr. 33%) by kinetic resolution of thecis,cis-diol4 a (easily accessible by reduction of3) with (+)--phenylbutyric anhydride and oxidation to3. From the results the absolute configurations and optical purities of3 and4 a could be deduced: (–)-(7S)-3 and (+)-(6S,6S)-4 a, resp.; []_D ^max1070^o and 115^o resp. These values were confirmed by application of theNMR-method to4 a-bis(O-methylmande late). The circular dichroism of these spiro compounds in the region of the ferrocene absorption band (around 440 nm) was recorded and is discussed.

---

---

Herrn Prof. Dr.H. Nowotny mit besten Wünschen zum Geburtstag gewidmet.

---

1.Mitt. (zugleich 55. Mitt. über Ferrocenderivate)H. Falk undW. Fröstl, Mh. Chem.102, 1259 (voranstehende Mitt.).     

Anomalin,a new natural pyranocoumarin

Summary A new coumarin C₂₄H₂₆O₇, which we have calledanomalin has been isolated from the roots ofAngelica anomala Avé-Lall. On the basis of its chemical properties, the results of a study of its saponification products and UV, IR, and NMR spectroscopy it has been established that anomalin is 2,2-dlmethyl-3,4-diangeloyl-3,4-dihydropyrano-5,6: 8, 7-cournarin.     

Spin crossover studies in tris(N,N′-dialkyldithiocarbamato)iron(III) complexes

A series of fifteen complexes of the type [Fe(RRNCS₂)₃] with symmetric (R=R=n- C₆H₁₃, n-C₈H₁₇, CH₂–CH=;CH₂, C₆H₅, C₆H₁₁ and C₆H₅CH₂), unsymmetric (R = CH₃; R = n-C₄H₉, C₆H₁₁, C₆H₅ and R = C₂H₅; R = n-C₄H₉, C₆H₁₁, C₆H₅ and i-C₃H₇) and ring substituents (RNR=pyrrolidyl and piperidyl) have been synthesized and their magnetic moments and Mössbauer spectra recorded from room temperature (RT) to liquid nitrogen temperature (LNT). Room temperature Mössbauer spectra of all the complexes exhibit an asymmetric doublet, which could be resolved into two doublets, each corresponding to low and high spin states in equilibrium. The crystal structure of tris(N, N-diallyldithiocarbamato)iron(III) shows it to be monoclinic with trigonally distorted octahedral geometry and space group C2/c. Fe–S stretching vibrations in the far i.r. region also show equilibria, HS LS. Depending on the nature of the alkyl group substituent, variable temperature magnetic moment and Mössbauer spectral studies, all the complexes may be divided into three groups; high spin complexes exhibiting spin-crossover (⁶A_1g ²T_2g), high spin complexes exhibiting spin transition (⁶A_1g ⁴T_1g) and intermediate spin complexes showing spin transition (⁴A_1g ²T_2g). On the basis of areas of the two doublets corresponding to high and low spin states, their percent contributions were calculated. Furthermore, magnetic moments of the equilibrium mixture calculated on the basis of respective areas compare well with the experimentally determined _eff values. E_Q values for both high and low spin states show linear decrease with increasing temperature.     

Five-membered 2,3-dioxo heterocycles: XLVIII. Reaction of 3-aroyl- and 3-heteroyl-2,4-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrolo[2,1-<Emphasis Type="Italic">c</Emphasis>][1,4]-benzoxazine-1,2,4-triones with 3-amino-5,5-dimethyl-2-cyclohexenone

3-Aroyl- and 3-heteroyl-2,4-dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with 3-amino-5,5-dimethyl-2-cyclohexenone to give 3-aroyl-4-hydroxy-1-o-hydroxyphenyl-6,6-dimethyl-2,2,3,4,5,5,6,7-octahydro-1H-indole-3-spiro-2-pyrrole-2,4,5-triones. The structure of the products was proved by X-ray analysis.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1405–1409.Original Russian Text Copyright © 2004 by Mashevskaya, Duvalov, Tolmacheva, Aliev, Maslivets.This study was performed under financial support by the Russian Foundation for Basic Research (project nos. 01-03-32641 and 02-03-96411).For communication XLVII, see [1].     

Kinetics and mechanism of the decomposition of hydrogen peroxide catalyzed by Mn(II)-bis-salicylaldimine complexes

Summary The tetradentateSchiff bases N,N-bis(salicylidene) ethylenediamine (salen), N,N-bis-(salicylidene) hexylenediamine (salhex), and N,N-bis(salicylidene)-o-phenylenediamine (sal-o-phen) are very strongly adsorbed by cation exchange resins (Dowex-50W) with manganese(II) as a counter ion, forming stable complexes. The kinetics of the catalytic decomposition of H₂O₂ in presence of these complexes has been studied in aqueous medium. The decomposition reaction is first order with respect to H₂O₂ in the case ofsalen andsal-o-phen and third order in the case ofsalhex. The greater the ligand methylene chain length or the greater the steric effect of the ligand, the greater will be the rate of reaction. The reaction is governed by the entropy of activation. A reaction mechanism is proposed.

---

Kinetik und Mechanismus der von Mn(II)-bis-Salicylaldimin — Komplexen katalysierten Zersetzung von Wasserstoffperoxid

Zusammenfassung Die teradentatenSchiffschen Basen N,N-bis-Salicyliden-ethylendiamin (salen), N,N-bis-Salicyliden-Hexylendiamin (salhex) und N,N-bis-Salicyliden-o-phenylendiamin (sal-o-phen) werden von Kationenaustauschen (Dowex-50W) mit Mangan(II) als Gegenion unter der Bildung stabiler Komplexe adsorbiert. Die Kinetik der katalytischen Zersetzung von H₂O₂ in Gegenwart dieser Komplexe wurde in wäßrigem Medium untersucht. Die Zersetzungsreaktion ist erster Ordnung bezüglich H₂O₂ in den Fällensalen undsal-o-phen und dritter Ordnung im Fall vonsalhex. Die Reaktionsgeschwindigkeit steigt mit der Länge der Methylenkette des Liganden und mit dessen Raumbedarf und wird von der Aktivierungsentropie bestimmt. Ein Reaktionsmechanismus wird vorgeschlagen.

     

Synthesis and SAM formation of water soluble functional carboxymethylcelluloses: thiosulfates and thioethers

Functional thiomethyl and thiosulfate derivatives of carboxymethylcellulose (CMC, DS = 0.9) were synthesized by nucleophilic displacement reactions. Alkylation of CMC by allyl glycidyl ether took mainly place at the primary positions of the cellulose backbone and yielded a 6-O-(3-allyloxy-2-hydroxypropyl)-CMC 1 with a partial DS of 3-allyloxy-2-hydroxypropyl substituents DSallyl of up to 0.43. Addition of tetrathionate to the allyl groups gave rise to 6-O-(2,3-bis(thiosulfato)propoxy-2-hydroxypropyl)-CMC 2. As the addition of tetrathionate was sluggish and incomplete, alternatively bromine was added and the resulting dibromide was substituted by thiosulfate. A 40% conversion of the allyl groups was achieved by this two-step procedure. On the other hand, the addition of bromine to 1 in aqueous solution almost quantitatively yielded the bromohydrin derivative which was converted by displacement reaction with thiosulfate to 6-O-(2-hydroxy-3-thiosulfatopropoxy-2-hydroxypropyl)-CMC 4. 6-Thiomethyl-6-deoxy-CMC 6 was synthesized by displacement reaction of 6-O-tosylcellulose with sodium methylsulfide and subsequent carboxymethylation of the cellulose backbone. A partial DS of thiomethyl substituents DSThM=0.65 exclusively at the primary positions was obtained. All functional CMC derivatives, 2, 4, and 6 were readily available in gram quantities, rather stable and highly water soluble for pH > 3. On gold surfaces they form self-assembled monolayers (SAMs) with thicknesses of 1.2 to 2.4 nm as determined by surface plasmon resonance (SPR).     

Neue N-Heterocyclen aus Enaminoketonen

The reaction of aliphatic or cyclic enaminoketones with pyridine or pyrimidine derivatives leads to pyrido[2.3-d]-pyrimidines (3 a-h), benzo[6.7]cyclohepta[1.2: 4.5]pyrido-[ [2.3-d]pyrimidines (6 a-c), benzo[f]pyrimido[4.5-c]isoquinolines (6 d-e), benzo[3.4]cyclohepta[1.2-c][1.6]naphthyridines (7 a) and naphtho[2.1-c][1.6]naphthyridines (7 b).     

Synthesen von Heterocyclen, 148. Mitt.: Zur Chemie der Biisochininone

Zusammenfassung Brombernsteinsäure reagiert mit Benzalanilin inDMF/POCl₃ zum 2,2-Diphenyl-4,4-biisochinolin-3,3 (2H, 2H)-dion (1a). Brombernsteinsäuredichlorid gibt mit dem Anil vorerst ein Addukt, welches beim Erhitzen in Nitrobenzol unter Abgabe von H₂O, HBr und H₂ ebenfalls in1 a übergeht. Analog können die Derivate1b-1k hergestellt werden, die in Lösung intensiv fluoreszieren.

---

Syntheses of heterocycles, CXLVIII: concerning the chemistry of bi-isoquinolones

Bromosuccinic acid reacts with benzylidene aniline inDMF/POCl₃ yielding 2.2-diphenyl-4.4-biisoquinoline-3.3 (2H, 2H)-dione (1a). Bromosuccinyldichloride and benzylidene aniline give firstly an adduct, which loses H₂O, HBr and H₂ to yield1 a, if heated in nitrobenzene. The derivatives1b-1k are obtained in a similar way and show in solution an intensive fluorescence.

---

---

J. R. Geigy AG, Basel, zum Patent angemeldet, CH 3-3253 am 3. Februar 1970.