Three lanthanide complexes with mixed salicylate and 1,10-phenanthroline: syntheses,crystal structures,and luminescent/magnetic properties

Three new lanthanide complexes incorporating salicylate (HSA or SA) and 1,10-phenanthroline (phen), Ln₃(HSA)₅(SA)₂(phen)₃ [Ln = Ho (1) and Er (2)], and Sm₂(HSA)₂(SA)₂(phen)₃ (3), have been synthesized. X-ray structural analysis reveals that 1 and 2 are isostructural with a trinuclear pattern, and 3 exhibits a binuclear structure. Comparison of the structural differences between 1/2 and 3 suggests that the identity of metal plays an important role in construction of such complexes. The magnetic properties of 1 are discussed. Moreover, 2 and 3 are both photoluminescent materials, and their emission properties are closely related to their corresponding Ln^III centers.     

Über Tetrahydro-6-methyl- bzw. 6-phenyl-2-oxopyrimidin-5-carbonsäuren und ihre Derivate Über Heterocyclen, 48 Mitt

Tetrahydro-6-methyl- and-6-phenyl-2-oxopyrimidine-5-carboxylic acids5, 8 resp are obtained on hydrogenolysis of the corresponding benzyl esters4, 7; 1-methyl compounds (5, 8) are also formed by hydrolysis of the ethyl and benzyl esters (3, 4, 6, 7) in alcoholic KOH. Benzyl esters4 which are unsubstituted at position1 are converted by alcoholic KOH into ethyl esters3. Phenols convert3, 4, 5, depending on the substituent in position 1, into 6-hydroxyphenyltetrahydro-2(1H)-pyrimidinones (10) or di(tri)phenylalkanes11, 12. Bromination of the pyrimidine-carboxylic acids5 or of the tert butyl esters18 leads to the 6-bromomethyl- and dibromomethyl derivatives15, 16, which are easily transformed into furo-[3,4-d]pyrimidines17. Thermal decarboxylation of carboxylic acids5 c, f, g lead to dihydro-2(1H)-pyrimidinones13 a, c, d.     

Studies on Spiroheterocycles,Part II: Heterocyclization of the Spiro Compounds Containing Cyclohexanone and Thiobarbituric Acid with Different Bidentate Nucleophilic Reagents

The reaction of thiobarbituric acid with different diarylidene ketones 1a–c yields the spiro compounds 2a–c. The diarylidene derivatives 3a–c are synthesized by the condensation of spiro compounds 2a–c with different aldehydes. A series of spiro heterocycles compounds 4a–l, 5a–l, 6a–l, 7a–l, 8a–l, and 9a–l are synthesized from the diarylidene compounds. The structures of the compounds are ascertained from their analytical and spectral data. Some of the compounds are screened for their biological activities.     

Synthesis of Modified Di- and Trisaccharide Fragments of N-Glycoproteins

Abstract

The syntheses of several analogues of disaccharide Manot(1→6)Mana-OCH₃ (1) and of trisaccharide Mana(1→6)[Mana(1→3)]Mana-OCH₃ (2) are reported. The syntheses are described of the diastereomeric 6-methyl derivatives 9a and 9b, which are representatives of fixed conformations of disaccharide 1. The syntheses of the 2-amino-2-deoxy analogues 15 and 17 and the synthesis of the 2-fluoro-2-deoxy analogue 28 are also reported.     

Darstellung und Kristallstrukturen halogenierter Carbonyl-derivate des Bicyclopentadienylidens

Treatment of dodecachlorobicyclopentenylidene1 with fuming nitric acid yields mainly octachlorobicyclopentenylidendione5 besides hexachloropentenylidentrione6. Both compounds are obtained as yellow crystalline solids. Octachlorobicyclopentadienylidene2 reacts with fuming nitric acid forming yellow -halo-nitro-carbonyl-compounds7 and8. Thermical cleavage of NOCl from7 in nitrobenzene leads to the orange tetrachlorobicyclopentenylidentetraone9. The molecular structures of7 and8 are derived from their ir and mass spectra, whilst the molecular structure of5,6 and7 are established by single crystal x-ray diffraction. Bond distances and angles are given and discussed.

     

Reaktionen von Arylidentetralonen mit Cyanessigsäurederivaten

Some reactions of 2-arylidene-tetralones1 with cyanoacetamide and alkyl cyanoacetates under basic conditions are described. From1 and cyanoacetamide the benzo[h]quinoline-2-ones3 are formed by cyclization with the carboxamide group, the intermediate addition product2 is not isolable. The addition products5 from1 and cyanoacetates however are crystalline compounds, which are converted by cyclization via the ester group to lactones6, and then oxidized to7. The expected products from a cyclization with the cyanide group are not found. The possibility of this cyclization path is shown by reaction of5 to the tetracyclus10 whose structure is found to be analogue to that of the reaction product from11-obtained by reaction from1 and malononitrile-to12.

3. Mitt.:H.-H. Otto, O. Rinus undH. Schmelz, Synthesis1978, 681.     

Synthesen von Alkyl-bzw. Cycloalkylpyridinen und Naphthyridinen

Condensation reactions of alkyl-and cycloalkylenaminoketones, resp. with cyanoacetamide, malononitrile and 2-amino-1-propene-1,1,3-tricarbonitrile (2) are investigated. Hydrolysis of dicyanomethylene substituted alkyl-dihydropyridines3 leads to 1,6-naphthyridines4 and5. With 2-morpholino-1-cyclohexenyl-1-ethanone (6) isoquinolines8 and9 are obtained. Condensation of 2-morpholinomethylene-cycloalkanones11 yields cycloalkanepyridines12 and13. 2-Morpholinomethylene-1,3-cyclohexanediones18 with malononitrile give the quinolinones20.     

Substituierte Methylphosphonate als Synthone für alicyclische α-funktionalisierte Phosphonate

Summary Syntheses of cycloalkylphosphonates4, and6–8 are described, starting from the substituted methylphosphonates1–3. Hydrolysis of the phosphonic esters4 and8 yield the free phosphonic acids5 and10; the partial hydrolysis of7 leads to easily accessible9. The benzo condensed phosphonates12 and13 are formed according to the solvent; a higher boiling medium should be used to obtain15 and17.

     

PHOSPHORORGANISCHE VERBINDUNGEN 1171, EINE NEUE METHODE ZUM NACHWEIS DER FUNKTIONELLEN GRUPPEN: OH,NH2 UND SH DURCH AUSLOSUNG VON FLUORESZENZ

Abstract

Covalently with a fluorescence support linked nitroarylester groups quench the fluorescence. The substitution of the fragment with the quenching group by an other functional group initiates fluorescence. If this substitution reaction is chemoselective, a reagent for the selective detection of a special functional group is available.

The non fluorescent compounds 1a and 1b are OH-(resp. F^(-)) selective; the compounds 5 and 7 are NH-selective and the compounds 8 and 9 are SH-selective. Dansyl-nitroimidazolide 7a discriminates between neutral and basic α-amino acids.     

Effects of metal ions and ligands on transesterification: synthesis,structures, and catalytic activities of a series of cation–anionic complexes with dipyridylamine ligands

A series of cation–anion complexes derived by 2,2′-dipyridylamine (Hdpa) and carboxylate ligands with formulas [Ni(Hdpa)₂(CH₃COO)]Cl(CH₃OH) (1), [Co(Hdpa)₂(CH₃COO)]Cl(CH₃OH) (2), [Ni(Hdpa)₂(CH₃CH₂CH₂COO)]Cl (3), [Co(Hdpa)₂(CH₃CH₂CH₂COO)]Cl (4), [Ni(Hdpa)₂(C₆H₅COO)]Cl (5), and [Co(Hdpa)₂(C₆H₅COO)]Cl (6), were synthesized and characterized by IR, elemental analysis, MS(ESI), TG analysis, UV-Vis, and fluorescence spectra. X-ray single crystal structural analysis showed that the coordination geometries of metal ions in these complexes are similar and they are cation–anion species. The hydrogen-bonding structures are 1-D chains through the N–H···Cl bonds. There are weak stacking interactions between pyridine rings in 1–4, while there are no stacking interactions in 5 and 6. We have investigated the transesterification of phenyl acetate with methanol catalyzed by 1–6 under mild conditions; 1–4 are homogeneous catalysts while 5 and 6 are heterogeneous catalysts due to their poor solubility in methanol. Cobalt complexes exhibit higher catalytic activities than corresponding nickel complexes. Complex 4 is the best catalyst of these six complexes.     

Studies on Phosphonium Ylides,XXIV: Reactions of Phosphorus Ylides with 1,2,3,4-Tetrahydro1-Naphthylidene-Malononitrile

1,2,3,4-tetrahydro-1-naphthylidene-malononitrile (1) reacts with carbethoxymethylene and carbmethoxymethylene- triphenylphosphoranes (2a, 2b) to give the new phospho-ranylidenecyclopentaylidene products (4a, 4b, and 5), respectively. The treatment of (1) with phosphorus ylide 2c afforded the new phosphonium ylide 6. Moreover, the application of reagent (2d) on (1) renders compound 7. On the other hand, when N-phenyliminotriphenylphosphorane (3) reacts with (1), the corresponding adduct (8) was obtained together with triphenylphosphine. Mechanisms accounting for the formation of new products are discussed, and probable structures of products are presented based on analytical and spectroscopic data.     

1-Phenylamino-2-imidazoline und 1,2,5,6-Tetrahydro-1,2,4-triazine aus N-(2-Chloralkyl)-imidchloriden

1-Phenylamino-2-imidazolines3 and 1,2,5,6-tetrahydro-1,2,4-triazines4, 5 and6 are synthesized from N-(2-chloralkyl)-imidchlorides1 and phenylhydrazines. As intermediates are obtained the hydrochlorides of amidrazones2 which cyclise. The structure of the different heterocyclic systems are determined by¹H- and¹³C-NMR-spectroscopy.

     

SYNTHESIS OF NATURALLY OCCURRING DIOSPHENOLS AND HYDROXYDIOSPHENOLS

ABSTRACT

Syntheses of diosphenol (3), ψ-diosphenol (4), 6-hydroxydiosphenol (5) and 6-hydroxy-ψ-diosphenol (6), which are constituents of the essential oil from Barosma betulina Bartl. (mountain buchu), are discussed.     

Coordination-driven synthesis of Ag(I) compounds based on a double emission ligand consisting of 1,3,4-oxadiazole and cyclotriphosphazene units

A new ligand (L) which consists of cyclotriphosphazene and 1,3,4-oxadiazole units is reported. Two new Ag(I) coordination compounds {[Ag(L)SO₃CF₃] _n (1) and Ag₂L₂(NO₃)₂ (2)} based on L and Ag(I) salts are obtained. Compound 1 features a 1-D chain, in which the ligand L adopts a divergent trans-conformation, whereas 2 is a discrete binuclear Ag(I) molecule in which L adopts convergent cis-conformation. Compounds 1 and 2 are fully characterized by ¹H-NMR, Infrared, elemental analysis, X-ray powder, and single-crystal diffraction. Luminescent properties of 1 and 2 are investigated.     

Synthesen von α,β-ungesättigten 2-(2-Oxo-benzazolin-3-yl)-3-hydroxy-dithio-carbonsäure-alkylestern und entsprechend substituierten Keten-S,S-acetalen sowie deren Kristall- und Molekülstruktur

Summary The new alkyl 2-(2-oxo-benzazoline-3-yl)-3-hydroxy dithiocrotonates and dithiocinnamates4 and the corresponding ketene dithioacetals2 and5 are obtained by dithiocarboxylation of the 3-acceptormethyl substituted benzazoline-2-ones1 or3. Alkylation at room temperature gives compounds4 whereas at higher alkylation temperature2 or5 are formed. The results of X-ray analyses performed for methyl 3-hydroxy-p-chloro-dithiocinnamate4d and of N-[1-(4-chloro-benzoyl)-2,2-bis(methylthio)-vinyl]-benzothiazoline-2-one5e are discussed.

     

A Closer Look at the Hydroiodination of Propiolic Acid

The crystal structures of cis‐3‐iodoacrylic acid (1), trans‐3‐iodoacrylic acid (2), trans‐3‐iodoacrylic acid methyl ester (3), 3,3‐diiodopropanoic acid (4), and trans‐2,3‐diiodoacrylic acid (5) are reported. Compounds 1 and 2 are the kinetic and thermodynamic products, respectively, of the hydroiodination of propiolic acid. Compound 4 results from addition of a second equivalent of hydroiodic acid to 1 or 2, whereas 5 results from the addition of trace elemental iodine to propiolic acid.     

Synthesis and spectral studies of nickel(II) complexes derived from disalicylaldehyde oxaloyldihydrazone

The mononuclear nickel(II) complex [Ni(H₂slox)(H₂O)₃] (1) and polymeric dinuclear complexes [Ni₂(slox)(A₄)] {A = H₂O (2), py (3), 2-pic (4), 3-pic (5) and 4-pic (6)} and the discrete binuclear complexes [Ni₂(slox)(NN)₃] {NN = bpy (7) and phen (8)} have been synthesized from disalicylaldehyde oxaloyldihydrazone (H₄slox) in methanol. All of the complexes are nonelectrolytes. Complexes 1, 7, and 8 are paramagnetic while binuclear 2–6 possess anomalously low μ _eff value, indicating considerable metal–metal interaction. Discrete binuclear 7 and 8 have no interaction between the two nickel(II) ions. The anomalously low magnetic moment values in 2–6 are explained as metal–metal interaction via phenoxide bridge. Such metal–metal interactions are less in 7 and 8 due to coordination of bipyridine and phenanthroline molecules which do not allow phenoxide bridging. The dihydrazone coordinates to the metal center as a dibasic tridentate ligand in keto-enol form in staggered configuration in 1, while in the remaining complexes the dihydrazone is tetrabasic hexadentate in enol form in anticis configuration. The metal center has a tetragonally distorted octahedral stereochemistry.     

OLEFIN SYNTHESIS VIA THE LITHIUM DERIVATIVES OF THE N,N,N,N′-TETRAMETHYLDIAMIDES OF ARYLMETHANEPHOSPHONIC ACIDS. 2. SYNTHESIS OF SOME (Z)-ORTHO-AND PARA-SUBSTITUTED STILBENES

Abstract

The reaction of the lithium derivatives of N,N,N′,N′-tetramethyldiamides of arylmethanephosphonic acids (1-Li) with ortho- and para-substituted benzaldehydes 2 is studied. Reaction conditions are found for erythro-stereoselective addition of 1 to 2 with high diastereomeric purity (95–99%) of the erythro adducts 3, 4 (yields 35–72%). By thermolysis of the adducts in neutral medium the corresponding (Z)-ortho and para-substituted stilbenes 5, 6 are obtained. Some factors causing the predominant formation of the erythro adducts 3, 4, as well as the influence of the ortho-substituents on the equilibrium threo-3, 4 ? erythro-3, 4 are discussed.     

Preparation and Reactions of 2-Oxa-6-thiabicyclo[3.2.0]-heptanes and 2-Oxa-5-thiabicyclo[2.2.1]heptanes from Pentoses

Abstract:

The preparation of the two diastereoisomeric 3-methoxy-2-oxa-6-thiabicyclo-[3.2.0]heptan-4-ols 4 and 5 from D-xylose 1 via methyl 2,3-anhydro-α-D-ribofuranoside and the corresponding β-anomer is described. Oxidation of 4 and 5 yields the sulfoxides 6 and 7 and the sulfones 8. – On the other hand, the two diastereoisomeric 3-methoxybicyclo[2.2.1]heptan-7-ols 11 and 12 are obtained from methyl 5-acetylthio-5-deoxy-2-O-mesyl-D-xylofuranosides 9 and 10 via Mitsunobu reaction and intramolecular cyclization. – The stereoisomeric counterparts of 4 and 5, 13 and 14, are obtained in only four steps from L-arabinose.     

THE STAUDINGER REACTION BETWEEN 2-H-1,2,3-DIAZAPHOSPHOLENES AND AROMATIC AZIDES

Abstract

The title reaction between substituted phenyl azides 2 and diastereomeric diazaphospholenes 1 gives the corresponding cyclic phosphazenes 3 with different stereochemical results. Hydrolysis of some phosphazenes 3 yield the corresponding ring-opened compounds Z-4I together with small amounts of diazaphospholene-oxide 5 and anilines 6. The configuration of the compounds obtained are established by ¹H n.m.r. spectroscopy. The results are explained invoking the formation of pentacoordinate phosphorus intermediates.