一些二茂铁苯基亚胺化合物的合成与表征

通过回流对应的二茂铁苯胺和芳香醛的混合物的同样路径合成了一系列新颖的二茂铁苯基亚胺化合物(5~12)。当暴露于空气时化合物5~12稳定,不发生任何分解。所有化合物均用¹H、¹³C NMR,MS,IR,UV-Vis和元素分析表征。还报导了化合物N-(3-bromo-2-hydroxylbenzylidene)-4-ferrocenylimine(10)的单晶结构,其结晶属单斜晶系P2₁/c空间群。     

一些二茂铁苯基亚胺化合物的合成与表征

通过回流对应的二茂铁苯胺和芳香醛的混合物的同样路径合成了一系列新颖的二茂铁苯基亚胺化合物(5~12)。当暴露于空气时化合物5~12稳定,不发生任何分解。所有化合物均用¹H、¹³C NMR,MS,IR,UV-Vis和元素分析表征。还报导了化合物N-(3-bromo-2-hydroxylbenzylidene)-4-ferrocenylimine(10)的单晶结构,其结晶属单斜晶系P2₁/c空间群。     

The effect of molecular polarity on nem/catic phase stability in 12-vertex carboranes

Weakly polar–polar isosteric pairs of 12-vertex p-carborane [closo-1,12-C₂B₁₀H₁₂] (1[12]) and monocarbaborate [closo-1-CB₁₁H₁₂]^? (2[12]) nematic liquid crystals, in which the difference in the calculated molecular dipole moment is 11.3 D, were synthesised, and the effect of the dipole moment on nematic phase stability was investigated. The trend observed for the 12-vertex series ([12]) was identical to that of the previously investigated 10-vertex series ([10]) containing [closo-1,10-C₂B₈H₁₀] (1[10]) and [closo-1-CB₉H₁₀]^? (2[10]): the uniform increase in the molecular dipole moment in the pairs of mesogens does not correspond to a uniform change in the clearing temperature, T_NI. This demonstrates the role of a remote substituent in modulating the intermolecular dipole–dipole interactions. The magnitude of such interactions was calculated (using density functional theory methods) for a pair of polar (2[12]d–2[12]d) and an analogous pair of weakly polar (1[12]d–1[12]d) molecules. All results for the 12-vertex series ([12]) were analysed relative to the 10-vertex analogues ([10]).     

Synthesis and photophysical behavior of thia-aza macrocycles with 9-anthracenylmethyl moiety as fluorescent appendage

1,3-Bis(bromomethyl)-2-methoxy-5-methylbenzene, 1,3-bis(bromomethyl)-2,4,6-trimethylbenzene, 1,3- and 1,4-bis(bromomethyl)benzene undergo nucleophilic substitution with methyl mercaptoacetate to provide respective diesters 6–9. These diesters (6–9) on stirring with bis(3-aminopropyl)amine and diethylenetriamine in methanol–toluene (1:1) mixture undergo intermolecular cyclization to give respective thia-aza macrocycles 10–15. The alkylation of macrocycles 10–13 with 9-anthracenylmethyl chloride gave amine N-(anthracenylmethyl) substituted macrocycles 16–19. The extraction profile of macrocycles 10–15 towards alkali (Li⁺, Na⁺, K⁺), alkaline earth (Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), Ag⁺, Tl⁺ and Pb²⁺ picrates shows preferential extraction of Ag⁺ with these macrocycles. The macrocycles 16–19 show fluorescence spectrum typical of anthracene moiety and depending on their structures exhibit 0–80 times increase in fluorescence on addition of transition metal ions. Fluorescent receptors 16, 17, and 19 are capable of functioning as a very efficient multi input OR logic gate.

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Graphical abstract 1,3- and 1,4-Bis(bromomethyl)benzene and its substituted derivatives undergo nucleophilic substitution with methyl mercaptoacetate to provide respective diesters 6–8. These diesters (6–8) on stirring with bis(3-aminopropyl)amine in methanol–toluene (1:1) mixture undergo intermolecular cyclization to give respective thia-aza macrocycles 10–12. The alkylation of macrocycles 10–12 with 9-anthracenylmethyl chloride gave amine N-(anthracenylmethyl) substituted macrocycles 16–18. The macrocycles 16–18 exhibit 0–80 times increase in fluorescence on addition of transition metal ions.

     

Synthesis and Spectroscopic Properties of S-,O-Substituted Naphthoquinone Dyes

New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were synthesized via vinilic substitution. 2,3-Dichloro-1,4-naphthoquinone gave 3a and 4b with 4,4′-thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction of 2,3-dichloro-1,4-naphthoquinone with cyclohexylmercaptane. The compounds 9d and 10 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-1,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro analysis, FT-IR, ¹H NMR, ¹³C NMR, MS, UV-Vis, and fluorescence spectroscopy.     

Novel discotic liquid crystal oligomers: 1,3,5-triazine-based triphenylene dimer and trimer with wide mesophase

Series of novel 1,3,5-triazine-based triphenylene oligomers 7, 10 and 12 with large bridging polyaromatic core were designed and synthesised by simple procedures in high yields. Their structures were confirmed by FTIR, ¹H NMR, ESI-MS and elemental analyses. Their mesomorphic behaviours were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. 1,3,5-triazine-based triphenylene monomer 7 has no mesomorphic property, but 1,3,5-triazine-based triphenylene dimer 10 and 1,3,5-triazine-based triphenylene trimer 12 possess excellent mesomorphic properties. The mesomorphic temperature range of compound 12 was as wide as 180°C. These studies indicated that the mesomorphic properties were determined by the numbers of triphenylene units. More units of triphenylene in the oligomers resulted in better mesomorphic properties.     

Room temperature liquid crystal of symmetric gallic trimer containing cyanuric core: synthesis and mesomorphism

Three novel gallic monomer 7, dimer 10 and trimer 12 with conjugated cyanuric core were designed and synthesised by Schiff-base condensation mode in yields of 80–90%. Their structures were characterised by fourier transform infrared spectroscopy, ¹H NMR (nuclear magnetic resonance), electrospray ionization mass spectrometry and elemental analyses. Their mesomorphic behaviours were investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The gallic monomer 7 has no mesomorphic property, but the dimer 10 and trimer 12 possess good mesomorphic properties. The trimer 12 with high symmetry exhibited the typical hexagonal columnar liquid crystal at room temperature. The temperature range of mesophase is as wide as 149°C (14–163°C). The results suggested that the more gallic units and symmetric structures are favourable for excellent mesomorphic properties.     

Synthesis,structure and luminescent properties of zinc(II) and Hg(II) complexes with substituted 1,10-phenanthroline

Two d¹⁰ group 12 metal complexes, 2-(2-methoxyphenyl)-1,10-phenanthroline zinc dichloride (2a) and 2-(2-methoxyphenyl)-1,10-phenanthroline mercury dichloride (2b) were synthesized and characterized by IR, ¹H and ¹³C NMR as well as elemental analysis. Structure of 2b in the solid state was determined by single-crystal X-ray crystallography, revealing that 2b is four-coordinate in a distorted tetrahedral geometry with the methoxy group uncoordinated. Luminescent properties of 2a and 2b in solution and the solid state were studied.     

Über die Darstellung von substituierten 3,4-Dihydro-2(1H)-pyrimidin-iminen und 2-Aminopyrimidinen aus Guanidin und α,β-ungesättigten Ketonen

Guanidine reacts with the 2-alken-1-ones4 a-f and5 to give the unstable dihydropyrimidinimines (or-amines respectively)8 a-f (I, II or III respectively) and the hexahydroquinazolinimine (-amine)9 (I, II or III);8 a-f lose H₂, partly in the course of the reaction, partly during recrystallization to yield the 2-pyrimidinamines10 a-c, e, f, and the 4-methyl-5,6,7,8-tetrahydro-2-quinazolinamine11. With picric acid the unstable compounds8 d, f and9, resp. are converted into the stable 2-amino-3,4-dihydro-1H-2-pyrimidinylium picrates12 d and into the 2-amino-4-methyl-3,5,6,7,8,8 a-hexahydro-1H-2-quinazolinium picrate (13 resp.14, 15)¹⁸, whereas8 e reacts with HCl to give the chloride12 e. The structures of12 d-f follow from their NMR-spectra, and of10 a-c, e, f and11 by alternative syntheses by known methods^12–17 (e.g. from -diketones and guanidine). The reaction of8 d-f and9 to10 d-f and11 respectively is compared with previously described dehydrogenation and disproportionation reactions, especially of 3,4-dihydro-2(1H)-pyrimidinones (6 d ⁴,23 ²⁰) and-thiones (30 ¹) of similar structure and formulated as a base-catalysed elimination of H₂.

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HerrnA. Fuchsgruber danken wir für die Aufnahme und Hilfe bei der Interpretation der NMR-Spektren.     

Phosphorus-Nitrogen Compounds: Part 25. Syntheses,Spectroscopic, Structural and Electrochemical Investigations,Antimicrobial Activities,and DNA Interactions of Ferrocenyldiaminocyclotriphosphazenes

Abstract

The condensation reactions of hexachlorocyclotriphosphazene (N₃P₃Cl₆) with mono (1 and 2) and bisferrocenyldiamines (3–5 and 7) resulted in the formation of tetrachloro mono- (8 and 9) and bisferrocenylspirocyclotriphosphazenes (10–13). In addition the tetramorpholino mono- (8a and 9a) and bisferrocenylphosphazenes (10a–12a) were obtained from the reactions of the corresponding tetrachlorophosphazenes (8–12) with excess morpholine. The structures of all the phosphazenes were determined using FTIR, MS, ¹H, ¹³C, and ³¹P NMR and 2-dimensional NMR techniques. The structures of 9a and 13 were determined by single crystal X-ray diffraction techniques. Cyclic voltammetric investigations of compounds 8a, 9a, and 11a revealed that ferrocene redox centers undergo reversible oxidation. These ferrocenylphosphazenes appear to be quite robust electrochemically. Interactions between the compounds 8a, 9a, 11a, and 12a and pBR322 plasmid DNA were investigated by agarose gel electrophoresis.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.]     

Organic Selenium Compounds,Part IV: Synthesis and Applications of Some New Diaryl Selenides Containing Azomethine and Oxazole Moieties

3,3′-Diacetyloxy (2), 3,3′-dihydroxy (3), 4,4′-diamino (4), and 4-amino (5) diphenylselenide derivatives were prepared as new precursors for the title studies. Compound 6 was obtained by condensation of 4 with an appropriate aromatic aldehyde. Unsymmetrical diphenylselenides 7 and 8 were obtained by condensation of 4 and/or 5 with an aromatic aldehyde. Compound 7 undergoes facile condensation with the same aldehyde present in its arylidene moiety to yield 6, while condensation with another different aromatic aldehyde yielded unsymmetrical 4-arylideneamino diphenylselenide derivative 9. Oxidation of 6, 8, and 9 using lead tetra acetate and/or N-bromosuccinimide yielded symmetrical bis-(2-aryl benzoxazol-6-yl) (10), unsymmetrical 3′-hydroxy, 2-aryl benzoxazol-6-yl selenides (11), and 2-aryl benzoxazol-6-yl, 2′-aryl′ benzoxazol-6′-yl selenide derivatives (12), respectively. Compound 10 was prepared in one-pot unequivocal synthesis by fusion of 4 with the appropriate aromatic aldehyde, while 12 was prepared by fusion of 4 with two different aromatic aldehydes. In certain cases, 6 and 9 were heated on a direct flame until complete homogeneity afforded the corresponding 10 and 12. The structures of the synthesized compounds are based on physical data, IR, ¹H NMR, ¹³C NMR, chemical means, and mass spectral data. Some of the synthesized compounds were biologically tested.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Syntheses,structures and catalytic activity for Friedel-Crafts reactions of substituted indenyl rhenium carbonyl complexes

The complexes [(η⁵-C₉H₆R)Re(CO)₃] [R = ⁿBu (8), ^tBu (9), CH(CH₂)₄ (10), Ph (11), Bz (12), 4-methoxyphenyl (13), 4-chlorophenyl (14)] were synthesized by refluxing substituted indenyl ligands [C₉H₇R] [R = ⁿBu (1), ^tBu (2), CH(CH₂)₄ (3), Ph (4), Bz (5), 4-methoxyphenyl (6), 4-chlorophenyl (7)], and Re₂(CO)₁₀ in decalin. The molecular structures of 9, 10, 12, and 13 were determined by X-ray diffraction analysis. These four crystals have similar molecular structures of the mononuclear carbonyl complex. In each of these molecules, Re is η⁵-coordinated to the five-membered ring of the indenyl group. Complexes 8–14 have catalytic activity for Friedel-Crafts reactions of aromatic compounds with a variety of alkylation and acylation reagents. Compared with traditional catalysts, these mononuclear metal carbonyl complexes have obvious advantages such as high activities, mild reaction conditions, high selectivity, and environmentally friendly chemistry.     

Photochemical arene exchange in the ferracarborane complex [1-(η-C6H6)-12-ButNH-1,2,4,12-FeC3B8H10]+

The benzene complex [1-(η-C₆H₆)-12-Bu^tNH-1,2,4,12-FeC₃B₈H₁₀]⁺ (3a) was synthesized by the photochemical reaction of [(η⁵-C₆H₇)Fe(η-C₆H₆)]⁺ (1) with the anion [7-Bu^tNH-7,8,9-C₃B₈H₁₀]⁻ followed by the treatment of ferracarborane 1-(η⁵-C₆H₇)-12-Bu^tNH-1,2,4,12-FeC₃B₈H₁₀ (2) with hydrochloric acid. The benzene ligand in cation 3a is replaced by alkyl-substituted benzenes under visible light irradiation in CH₂Cl₂ to form [1-(η-C₆R₆)-12-Bu^tNH-1,2,4,12-FeC₃B₈H₁₀]⁺ (3b–e; C₆R₆ is toluene (b), mesitylene (c), hexamethylbenzene (d), or anisole (e)). The structure of [3c]PF₆ was established by X-ray diffraction.     

Heterocalixarenes. Part 2. Calix[m]uracil[n]benzimidazol-2(1H)-one[3] arenes: Synthesis and Binding Characteristics

The reactions of uracil/benzimidazol-2(1H)-one with 1,3-bis(bromomethyl)benzene provide respectively1 3-bis[(3-bromomethylbenzene)methyl]uracil/benzimidazol-2(1H)-onewhich on subsequent cyclization with1,3-bis[(uracil-1-yl/benzimidazol-2(1H)-one-1-yl)methyl]benzenederivatives provide respectively calix[m]uracil[n]benzimidazoI-2(1H)-one[3]arenes[m =3, n = 0 (9); m = 2, n = 1 (10);m = 1, n = 2 (11) and m = 0, n = 3 (12)]. The heterocalixarenes 9–12, both in liquid–liquid and solid–liquid extraction experiments, selectively extract ammonium picrates over the similarly sized K⁺ picrate. The selectivity is much more pronounced in the case of solid-liquid extractions. Both in L-L and S-L extractions, 10 exhibits the highest order oft-BuNH₃ ⁺/K⁺ selectivity.     

1,2-Dipyridazinyl-?then- und-?than-1,2-diole aus Pyridazin-carbaldehyden

Treatment of pyridazine-4-carboxaldehyde with catalytic amounts of KCN results in formation of pyridazine-4-carboxylic acid and two stereoisomeric diols (4,5). The configurations of4 and5 are explained on basis of the¹H-NMR-spectra, the mechanism of reaction is discussed. Pyridazine-3-carboxaldehyde (10) reacts with HCN to form the addition product of10-cyanhydrine to10 (11). HCN-elimination from11 yields the enediol12 which by oxygen is oxidized to pyridazine-3-carboxylic acid or its methyl ester.     

Platinum–Ruthenium Cluster Complexes from the Reaction of Ru<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> with Pt(PBu<Superscript>t</Superscript><Subscript>3</Subscript>)<Subscript>2</Subscript>

Three new platinum–ruthenium complexes: Pt₃Ru₃(PBu^t ₃)₃(CO)₁₂, 8, Pt₅Ru₃(PBu^t ₃)₃(CO)₁₂, 9 and PtRu₃(PBu^t ₃)₂(CO)₈(μ₃-PBu^t)(μ-H)₂, 10 were obtained from the reaction of Ru₃(CO)₁₂ with Pt(PBu^t ₃)₂. Compound 8 was obtained from this reaction when conducted at 25 °C. Compounds 9 and 10 were obtained when the reaction was conducted at 68 °C. The structure of 8 consists of a central triangular cluster of three ruthenium atoms with one Pt(PBu^t ₃) group bridging each of the three Ru–Ru bonds. The structure of 9 consists of a capped pentagonal bipyramidal cluster of eight metal atoms that is formed formally by the addition of two platinum atoms to 8. The structure of 10 contains a triangular cluster of three ruthenium atoms with a Pt(PBu^t ₃) group bridging one of the Ru–Ru bonds. A t-butyl phosphido ligand formed by degradation of a molecule of PBu^t ₃ bridges the three ruthenium atoms. This report is dedicated to the memory of Professor F. A. Cotton for his many pioneering contributions to inorganic and metal cluster chemistry.     

Novel Hydrogen Transfer Reactions to the Ligated 1,2,4-Triphosphole in [Ru(η4-C8H12){η-P3C2But 2CH(SiMe3)2}]

INTRODUCTION

As discussed in a recent preliminary publication¹, the complex [Ru(η⁴-C₈H₁₂){η-P₃C₂Bu^t ₂CH(SiMe₃)₂}] (1) (C₈H₁₂ = cycloocta-l,5-diene) was prepared by the reaction of [Ru(η⁶-C₁₀H₈)(η⁴-C₈H₁₂)] (2) (C₁₀H₈ = naphthalene) with the 1,2,4-triphosphole P₃C₂Bu^t ₂CH(SiMe₃)₂ (3) (Fig. 1), illustrating the aromatic behaviour of (3).     

Synthesis and characterization of stannacyclododecane-yl-dithiocarbamates

Thirteen new stannacyclododecane dithiocarbamate complexes have been prepared by reacting 12-chloro-12-n-butyl-1,11-dioxa-4,8-dithia-12-stannacyclododecane (1) and 12-chloro-12-n-butyl-1,4,8,11-tetrathia-12-stannacyclododecane (2) with pyrrolidine-, morpholine-, thiomorpholine-, piperidine-, piperazinebis-, and 3-pyrroline-carbodithioates, respectively, as well as with diethyl-dithiocarbamate. All complexes were characterized by elemental analyses, IR, EI-MS, and NMR (¹H, ¹³C, and ¹¹⁹Sn) studies. The spectroscopic data suggest the replacement of the chlorides by the corresponding dithiocarbamates with monodentate coordination, leading to six-coordinate tin atoms in all the cases.     

The Synthesis and Properties of New Metal-free and Metallophthalocyanines Containing Four Diloop Macrocyclic Moieties

The synthesis and characterization of new metal-free (9) and metal-containing (Zn, Ni or Cu 10, 11, 12) derivatives of a symmetrically octasubstituted phthalocyanine derived from 21,22-dicyano-2,3,5,6,8,9,11,12,15,17,18,25,26,28-tetradecahydro[1,4,7,12] benzodioxadithiacyclotetradeceno[6,7-b][1,4,7,10,13]benzopentaoxacyclopentadecene (7), which was synthesized in a multi-step reaction sequence, have been described. The novel compouds have been characterized by a combination of elemental analysis, ¹H and ¹³C NMR, IR, UV–vis and MS spectral data.     

Reactions of Icosahedral Carboranes with Iminotris(dimethylamino)Phosphorane HNP(NMe2)3: a Deboronation Intermediate nido-C2B10H12·N(H)P(NMe2)3, Deboronation Reactions and Hydrogen-bonded Closo-carborane Systems

Reactions between the icosahedral carboranes 1,2-C₂B₁₀H₁₂ (1), 1,7-C₂B₁₀H₁₂ (2) and 1,12-C₂B₁₀H₁₂ (3) and the iminophosphorane HNP(NMe₂)₃ (4) are described that have afforded a variety of products whose structures have been characterised by X-ray diffraction. They include the adduct between (1) and (4), C₂B₁₀H₁₂·HNP(NMe₂)₃ (5) the 12-atom 14-skeletal pair supra-icosahedral nido structure of which illustrates an early step in the deboronation of ortho-carborane (1) by Lewis Bases, and the C–H⋯N hydrogen-bonded adducts of meta- and para-carborane with the iminophosphorane, [1,7-C₂B₁₀H₁₂⋯HNP(NMe₂)₃] _n and 1,12-C₂B₁₀H₁₂ 2HNP(NMe₂)₃. The iminophosphorane (4) readily converts ortho-carborane (1) into the nido anion [7,8-C₂B₉H₁₂]⁻ and less readily meta-carborane (2) into the nido-anion [7,9-C₂B₉H₁₂]⁻, which have been isolated from solution as salts of the cations [H₂NP(NMe₂)₃]⁺ or [{(Me₂N)₃PN}₂BNHP(NMe₂)₃]⁺, the latter evidently incorporating a boron atom removed from the carborane cage. Adventitious presence of water in the attempted recrystallization of [{(Me₂N)₃PN}₂BNHP(NMe₂)₃]⁺ [7,8-C₂B₉H₁₂]⁻ led to a salt of the cation [{(Me₂N)₃PNBN(H)P(NMe₂)₃}₂O]²⁺. Other unexpected products isolated from reactions carried out under moist air included the salt [H₂NP(NMe₂) ₃ ⁺ ]₂[CO ₃ ²⁻ ]·2B(OH)₃ (from the reaction between 2 and 4) and the salt 1,12-C₂B₁₀H₁₂·2H₂NP(NMe₂) ₃ ⁺ HCO ₃ ⁻ (from the reaction between 3 and 4).Dedicated to Prof. Brian F.G. Johnson, in recognition of his major contributions to cluster chemistry and warm friendship over the years.