Nouvelle Synthese Des 2-Thioxoethylphosphonates, 2- mercaptovinylphosphonates, 2-Phosphoryl-3-thioxopropanoates, 2-Thiomethylvinylphosphonates, 2-Thioethoxycarbonylmethylvinylphosphonates

The cyanomethylphosphonates 1 and the ethyl phosphoacetates 2 were reacted with some fluorophenylisothiocyanates to give the 2-thioxoethylphosphonates 3 in tautomeric equilibrium with the corresponding 2-mercaptovinylphosphonates 3 ′ and the 2-phosphoryl-3-thioxopropanoates 4 , respectively. Reaction of the cyanomethylphosphonates 1 with fluorophenylisothiocyanates in presence of methyliodide furnished the 2- thiometylvinylphosphonates 5 . The 2-mercaptovinylphosphonates 3 ′ reacted with ethyl chloroacetate in refluxing ethanol in the presence of triethylamine to give S-substitued derivatives 6 .     

Prearranged Glycosides,Part 10. Intramolecular Glycosylation with Cellobiosyl,Lactosyl, and Maltosyl Donors

ABSTRACT

Acetyl protected 1,2-O-(1-methoxyethylidene)-disaccharides 1 of maltose, cellobiose, and lactose, respectively were converted via the corresponding benzyl protected couterparts 2, the benzyl protected phenyl 2-O-acetyl- 3 and 2-O-unprotected 1-thio-glycoside disaccharides 4 into 2-O-succinoylated disaccharides 5. The latter were esterified with benzyl 2-O-benzoyl-4,6-di-O-benzylidene-α-D-glucopyranoside (6) to afford succinyl linked derivatives 7 the benzylidene groups of which were regioselectively opened to give prearranged glycoside trisaccharides 8. Intramolecular glycosylation of the latter with N-iodosuccinimide resulted in exclusive formation of the corresponding α-(1→4)-linked trisaccharides 9. No influence of the donor moiety on the diastereoselectivity of the intramolecular glycosylation was observed.     

Candidate Trail Attractants of Reticultermes lucifugus: Stereoselective Syntheses of (3Z, 6E,BE)-(3Z, 6E, 8Z)-and (3Z, 6Z, 8Z)-3,6,8 -Dodecatrien-1-OL1

Stereoselective syntheses on a gram scale of (3Z,6E,8E)-, (3Z,6E,8Z)-and (3Z,6Z,8Z)-3,6,8-dodecatrien-1-ol, 8, 9 and 10, respectively, are described. A key step of the synthesis of 8 consisted of a copper-mediated coupling reaction between 4-(2-tetrahydropyranyloxy)-1-butynylmagnesium bromide (15) and the mesyl ester of (2E,4E)-2,4-octadien-1-ol (14). A similar copper-mediated reaction between 15 and the mesyl ester of (E)-2-octen-4-yn-1-ol (19) was used to construct the C-12 carbon skeleton of 9. On the other hand, the synthesis of 10 was based on a palladium-promoted reaction between (Z)-1-bromo-1-pentene (23) and the organozinc bromide derived from 3,6-heptadiyn-1-yl acetate (27).     

Syntheses,structures, and thermal properties of new Au(III) organometallic compounds with ancillary S-, O-, and/or N-donor ligands

((CH₃)₂Au)₂C₂O₄ (1), ((CH₃)₂AuSCN)₂ (2), (CH₃)₂AuSSP(OCH₃)₂ (3), and (CH₃)₂AuSSP(OC₂H₅)₂ (4) were prepared and recrystallized from hexane to determine their crystal structures and analyze them by thermal methods (TGA). The compounds have been investigated as new possible precursors for metal–organic chemical vapor deposition (MOCVD). Compounds 1 and 2 are solids, while 3 and 4 are liquids. Crystal structures of 1 and 2 have been studied by single-crystal X-ray diffraction (XRD): compounds are monoclinic, space group for 1 P2₁/c, for 2 P2₁/n. Compound 1 has crystal parameters a?=?7.6952(5)?Å, b?=?11.1814(8)?Å, c?=?12.2893(8)?Å, α?=?90°, β?=?104.922(4)°, γ?=?90°; 2 has crystal parameters a?=?5.6184(3)?Å, b?=?15.2744(6)?Å, c?=?6.9202(3)?Å, α?=?90°, β?=?102.864(2)°, γ?=?90°. These are neutral complexes, in which molecules are only connected by van der Waal's interactions. Thermal gravimetric analyses (TGA) have shown that 3 and 4 evaporate practically without decomposition. MOCVD experiments were carried out at lower pressure using 3 and 4 as precursors. The films were grown on Si substrate and investigated by XRD and SEM.     

The easy hydrolysis of hexacyanocyclopropane, ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate, 1,2,2,3,3-pentacyanocyclopropane-1-carboxamide, andN,N-dimethyl-1,2,2,3,3-pentacyanocyclopropane-1-carboxamide tor-1,c-2,c-3-tricyanocyclopropane-t-carboxamide

Hydrolysis of hexacyanocyclopropane (1a), ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate (1b), 1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1c), andN,N-dimethyl-1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1d) in 95% acetic acid yieldsr-1,c-2,c-3-tricyanocyclopropane-t-1-carboxamide (3). The structure of3 was proved by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 454–456, March, 1998.     

Synthesis of Polyfunctionally Substituted Pyrazolonaphthyridine,Pentaazanaphthalene, and Heptaazaphenanthrene Derivatives

6-aminopyrazolo[3,4-b]pyridine-5-carbonitrile (2) was used as a precursor for the synthesis of a variety of pyrazolo[3,4-b][1,8]naphthyridines (3, 4) and pentaazacyclopenta[b]naphthalenes (5–10, 13, 14) via the initial addition to either the cyano or amino group followed by cyclization. Also, a series of heptaazadicyclopenta[a,g]naphthalenes (15–17) and heptaazacyclopenta[b]phenanthrenes (18, 19) were obtained via the interaction of 4-(dibenzothiophen-2-yl)-1,5-dihydro-5-imino-3-methyl-1-phenyl-1,2,6,8,9-pentaazacyclopenta[b]naphthalen-6-ylamine (14) with different reagents. The structures of the synthesized compounds were established by elemental and spectral analyses.     

A new trans-dioxorhenium(V) complex with 4-aminopyridine: synthesis,structure, electrochemical aspects,DFT, and TD-DFT calculations

The reaction of 1?:?4.4?M proportion of cis-[ReO₂I(PPh₃)₂] and 4-aminopyridine (ampy) in acetone–water gives trans-[ReO₂(ampy)₄]I·2H₂O (1a) in 85% yield. 1a has been characterized by C, H, and N microanalyses, FT-IR, UV–vis, ¹H NMR spectroscopy, and molar conductivity. The X-ray crystal structure of 1a reveals an octahedral trans dioxorhenium(V) complex with a “N₄O₂” coordination for rhenium. 1a has an orthorhombic space group C2221 with a?=?17.576(4), b?=?19.370(4), c?=?15.730(4) Å, V?=?5355(2) ų, and Z?=?8. Geometry optimization of the trans-O,O complex, 1a and its cis-O,O analog, 1b performed at the level of density functional theory reveal that 1a is more stable than 1b by 25?kcal M^–1 in the gas phase. The electronic spectrum of 1a was also analyzed at the level of time-dependent density functional theory. Excitation of 1a in methanol at 450?nm leads to a fluorescent emission at 505?nm with a quantum yield (Ф) of 0.04. Electrochemical studies of 1a in acetonitrile show a quasi-reversible Re(V) to Re(VI) oxidation at 0.618?V versus Ag/AgCl. This redox potential matches with the calculated redox potential of 0.621?V versus Ag/AgCl.     

Utility of Hydrazinopiperidinomethanethione in Synthesis of Thiadiazole,Thiadiazine, and Pyrazole Derivatives

Hydrazinopiperidinomethanethione 2 was prepared and reacted with active halo compounds, carbon disulfide, phenyliso-thiocyanate, ylidenenitriles, and N,S-acetyls to give thiadiazine 4–7 , thiadiazole 8–10 , and pyrazole 11,13 , 14–17 derivatives, respectively.     

Total synthesis of (3Z,9Z,6S,7R) and (3Z,9Z,6R,7S)-6,7-epoxy-3,9-octadecadienes

(3Z,9Z,6S,7R)-6,7-epoxy-3,9-octadecadiene (1) and (3Z,9Z,6R,7S)-6,7-epoxy-3,9-octadecadiene (2) have been stereoselectively synthesized in eight steps from 2-pentyn-1-ol with an overall yield of 8%. The key steps involved the Sharpless asymmetric dihydroxylation of (2E)-oct-2-en-5-yn-1-ol (6). The new synthetic method is suitable for multigram-scale preparation of 1 and 2 and might be used for producing sufficient quantities of the sex pheromone components for management of the pest of tea plantations.     

Synthesis of Benzo[b]thiophene Substituted Carbamates,Ureas, Semicarbazides,and Pyrazoles and Their Antimicrobial and Analgesic Activity

2-Azidocarbonyl-3-chlorobenzo[b]thiophene 3 was obtained from 3-chloro-benzo[b]thiophene-2-carbonyl chloride 1 and 3-chloro-benzo[b]thiophene-2-carboxy hydrazide 2 . The compound 3 on Curtius rearrangement with various alcohols, amines, and hydrazines afforded the corresponding carbamates 4a–b , ureas 5a–j , and semicarbazides 6a–g , respectively. Compound 2 was also utilized for the synthesis of pyrazoles 7a–c by treatment with various chalcones. The structures of the newly synthesized compounds were elucidated on the basis of IR, ¹ H NMR, and mass spectral data and have been screened for antimicrobial and analgesic activities.     

Synthesis,spectroscopic studies,antimicrobial activity,and crystal structure of a Zn(II) complex based on Voriconazole

[Zn(FZ)₂Cl₂] (1) (FZ = Voriconazole, (2R,3S)-2-(2,4-difluorophenyl)-3(5-fluoropyrimidin-4-yl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol), has been obtained through the reaction of zinc chloride and FZ and has been characterized by FT-IR, UV–vis and fluorescence spectra, elemental analysis (EA), single crystal X-ray diffraction, powder X-ray diffraction and thermogravimetric analysis (TGA). FZ was also characterized by FT-IR, UV–vis spectra, single crystal X-ray diffraction and TGA. FZ crystallizes in the chiral space group P2₁ and 1 crystallizes in chiral space group P₁ with a mononuclear structure. In 1, there are three kinds of hydrogen bonding interactions and weak stacking interactions which generate a 3-D architecture. The primary antimicrobial results show that 1 exhibits potent activity against Aspergillus (Aspergillus niger, Aspergillus terreus, Aspergillus fumigatus and Aspergillus flavus) and Candida species (Candida albicans, Candida krusei, Candida glabrata and Cryptococcus neoformans), higher than that of free FZ. Fluorescence spectra of 1 and FZ have been discussed.     

Cyano-complexes and salts with tetracyanonickellateII and N,N-bis(2-hydroxyethyl)-ethylenediamine: synthesis,IR spectra,magnetic properties,thermal analyses,and crystal structures

Four cyano complexes, [Ni(N-bishydeten)Ni(CN)₄] _n (c1), [Cu(N-bishydeten)₂][Ni(CN)₄] (c2), [Zn₂(N-bishydeten)₂Ni(CN)₄] _n (c3), and [Cd(N-bishydeten)₂][Ni(CN)₄] (c4), have been synthesized and characterized by FT-IR, elemental, and thermal analyses. The structures of c2 and c4 were determined by single-crystal X-ray diffraction studies; both structures contain isolated cations and anions. The c2 consists of [Cu(N-bishydeten)₂]²⁺ with octahedrally coordinated Cu^II and diamagnetic [Ni(CN)₄]^2–, but c4 consists of [Cd(N-bishydeten)₂]²⁺, in which Cd^II is eight coordinate with two tetradentate N-bishydeten and diamagnetic [Ni(CN)₄]^2–. The value of the shape measure S (^o) indicates that the coordination geometry around Cd^II lies along D _2d [dodecahedron; (dd)], C _2v [bicapped trigonal prism; (btp)], and D _4d [square antiprism; (sap)] but close to D _2d and D _4d. Variable temperature magnetic susceptibility measurements of c1 and c2 show the presence of little antiferromagnetic interaction below 20?K. Thermal analyses reveal that first neutral N-bishydeten and then cyano ligands were liberated from the complexes.     

Tricarbonylchromium complexes with phenalene. Synthesis, structure, and thermal rearrangements

The reaction of phenalene with Cr(CO)₃Py₃/BF₃·OEt₂ afforded a mixture of two isomeric complexes, tricarbonyl(6a,7-9,9a,9b-·⁶-phenalene)chromium (1) and tricarbonyl(3a,6a,9b,4-6-·⁶-phenalene)chromium (2). Deprotonation of the mixture of compounds1 and2 followed by treatment with MeI, BuⁿI, or D₂O gave complexesexo-1-R-1 (3–5: R=Me (3), Buⁿ (4), or D (5)). The molecular geometry of complex3 was established by X-ray structural analysis. Heating of complex5 in toluene or C₆F₆ at 90–110 °C resulted in redistribution of deuterium among positionsexo-1,endo-1, and 3 in the resulting complexes of types1 and2 via sigmatropic shifts of the H _exo and H _endo atoms in the nonaromatic ring as well asvia inter-ring migrations of the tricarbonylchromium group. In the case of3, the methyl label is distributed among positionsexo-1 and3 to form isomeric complexes with similar structures (exo-1-Me-2 (6), 3-Me-2 (7), and 3-Me-1 (8), respectively)via processes analogous to those observed in the case of isomerization of compound5 (except for migration of the H _exo atom). The mechanisms of these rearrangements are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1863–1880, October, 1997.     

Theoretical Studies on S-Phenyl-thiabenzene,S-Phenyl-thianaphthalene,and S-Phenyl-thiaanthracene

The molecular structures of S-phenyl-thiabenzene 1, S-phenyl-1-thianaphthalene 2, S-phenyl-2-thianaphthalene 3, and S-phenyl-9-thiaanthracene 4 are studied by ab initio calculations using HF as well as DFT methods at the 6–311+G? level of theory. The non-planar boat conformers of 1–4 with 6π electrons in the heterocyclic ring appear to be more stable than the corresponding planar conformers with 8π electrons in the ring. The activation energy for the inversion at the sulfur atom is compared for 1–4. Conformational flexibility of 1–4 is studied.     

Design,synthesis, and antimicrobial activities of new tanshinone IIA esters

Sixteen new ester derivatives with various partition coefficient (ClogP) values of tanshinone IIA (TSIIA), a major lipophilic component of Salvia miltiorrhiza, were designed and synthesised, including six aliphatic esters (3a–e, 5a), one phosphate ester (4c) and nine aromatic esters (5b–j). Their antimicrobial activities against three Gram-positive bacteria strains, Staphylococcus aureus, Bacillus subtilis, and Bacillus amyloliquefaciens, and two Gram-negative bacteria strains, Pseudomonas aeruginosa and Escherichia coli, as well as two fungi species, Candida albicans and Saccharomyces cerevisiae, were evaluated in vitro by broth microdilution susceptibility tests. The results showed that keeping ClogP values in a certain range is necessary for their antimicrobial activities. For those compounds with ClogP values between 5 and 10, their MIC values showed positive correlations with ClogP values. In particular, compound 3e exhibited fourfold and twofold higher potency than the standard drug amphotericin B against fungi C. albicans and S. cerevisiae with MIC values of 1.95 and 7.81 μg/mL, respectively.     

Synthesis,structural, photophysical and thermal properties of some praseodymium(III) complexes

Some carboxylato-bridged praseodymium(III) complexes (1–5) having tp [hydrotris(pyrazol-1-yl)borate] and sodium p-X-benzoate (where X =?H, F, Cl, NO₂) have been synthesized and characterized by different techniques including X-ray crystallography. The X-ray studies demonstrated that 1, 3 and 5 crystallized in triclinic space group P 1 with cell dimensions a =?11.761(13) Å, b =?12.536(13) Å, c =?17.726(19) Å for 1, a =?9.309(8) Å, b =?12.667(11) Å, c =?14.421(12) Å for 3, a =?11.5688(9) Å, b =?12.0055(9) Å, c =?12.3005(10) Å for 5. In 1–4 the coordination number of praseodymium is seven, whereas in 5 it is eight. IR suggested that the benzoate groups in 1–5 are bidentate bridging. The photophysical properties of these complexes have been studied in solution at room temperature. Thermogravimetric analysis showed that these complexes undergo complete decomposition with formation of praseodymium oxide.     

Synthesis,structure, electrochemical properties,and antioxidant activities of copper(II) and zinc(II) complexes with N,N-bis(N-ethyl-2-ylmethylbenzimidazol)allylamine ligand

N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline (EtAIDB) and its transition metal complexes, [Cu(EtAIDB)Br₂]·EtOH {dibromo[N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline] copper(II) ethanol} (1) and [Zn(EtAIDB)Br₂] {dibromo[N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline] zinc(II)} (2), have been synthesized and characterized by elemental analysis, molar conductivity, UV–visible, and IR spectroscopy. The X-ray crystallographic studies of 1 and 2 have shown two different arrangements: 1 is distorted square-based pyramidal, while 2 can be treated as distorted tetrahedral. The cyclic voltammogram of 1 represents quasi-reversible Cu²⁺/Cu⁺ pairs. In vitro antioxidant tests showed that 1 had significant antioxidant activity against superoxide and hydroxy radicals.     

Condensed thiazoles,II: Synthesis of 7-substituted thiazolo[4,5-d]pyrimidines as possible anti-HIV,anticancer, and antimicrobial agents

Summary Some 3-substituted 2-thioxothiazolo[4,5-d]pyrimidin-7(6H)-ones (2a,b;4) have been synthesized and converted to their 7-chloro (3,5), 7-diethanolamino (6a,b), 7-bis(2-chloroethyl)amino (7), 7-azido (8), 7-amino (9), 7-hydrazino (16), 7-mercapto (11a,b), and 7-methylthio (12) derivatives. These compounds were evaluated for theirin vitro antimicrobial, anti-HIV; and anticancer activities.For part I of this series, see Monatsh Chem127: 1203     

Condensed thiazoles,I: Synthesis of 5,7-disubstituted thiazolo[4,5-d]pyrimidines as possible anti-HIV,anticancer, and antimicrobial agents

Summary A convenient and simple synthesis of 5-mercapto-3-phenyl-2-thioxo-2,3-dihydrothiazolo-[4,5-d]pyrimidin-7(6H-one(2) and its 5,7-dichloro (3), 5,7-diazido (4), 5,7-diamino (5), 5,7-dimerapto (6), 5,7-dimethylthio (7), and 6-methyl-5-methylthio (8) derivatives is described. The prepared compounds were screened for theirin vitro anti-HIV, anticancer, antibacterial and antifungal activities.

---

Kondensierte Thiazole, 1. Mitt.: Synthese von 5,7-disubstituierten Thiazolo[4,5-d]pyrimidinen als potentielle anti-HIV, anticancerogene und antimikrobielle Verbindungen

Zusammenfassung Die Synthese von 5-Mercapto-3-phenyl-2-thioxo-2,3-dihydrothiazolo[4,5-d-pyrimidin-7(6H)-on (2) und seiner 5,7-dichloro-(3), 5,7-diazido-(4), 5,7-dimanio-(5), 5,7-dimercapto-(6), 5,7-dimethylthio- (7) und 6-methyl-5-methylthio-Derivaten (8) wird beschrieben. Die hergestellten Verbindungen wurden auf ihrein vitro anti-HIV, anticancerogenen, antibakteriellen und antimykotischen Aktivitäten geprüft.