Synthesis and polymerization of coupled compounds of 1,11-dodecadiyne

The dimer, trimer, and tetramer of 1,11-dodecadiyne, HC?C? (CH₂)₈? C?CH, were synthesized. The solid-state polymerization of the dimer was investigated by infrared (IR) spectroscopy. IR bands due to the diacetylene moiety were identified through the comparison of the IR spectra of the dimer, trimer, and tetramer. The dimer was found to have two polymorphs, melt-crystallized and solution-crystallized. Both of the polymorphs undergo solid-state polymerization by exposure to γ-ray or UV irradiation. The former has higher polymerizability for the diacetylene moiety than the latter. The solid-state polymerization of the terminal acetylene group was not observed. It is shown that the previously reported dimer structure in which both the diacetylene and terminal acetylene groups are polymerized to form an inherently electrically conducting polymer is incorrect. © 1995 John Wiley & Sons, Inc.     

Efficient One-Pot Synthesis of Tetrahydrobenzo[c]xanthene-1,11-dione Derivatives Under Microwave Irradiation

An efficient one-pot condensation of 4-hydroxylcoumarin, aromatic aldehydes, and 5,5-dimethylcyclohexane-1,3-dione has been achieved with molecular iodine as a catalyst via conventional heating and microwave irradiation techniques, and thus a variety of new tetrahydrobenzo[c]xanthene-1,11-dione derivatives were prepared in good yields.     

Reaction of benzoquinones and naphthoquinones with 1,8-diamino-3,6-dioxanonane and with 1,11-diamino-3,6,9-trioxaundecane

Reaction of 1,4-naphthoquinone or 2,3-dichloro-1,4-naphthoquinone with α,ω-diamino-derivatives of poly(alkylenoxides) leads to the formation of α,ω-bis(quinonyl) amines. A similar reaction with chloranil, bromanil, dichlorodicyanobenzoquinone, S-phenylbenzoquinone and 1,4-benzoquinone itself, leads to the formation of quinoid crown ethers.     

New 1,11-dimethyl-3,6,9-triazatricyclo[7.3.1.13,11]tetradecane-4,8,12-trione derivative as an allosteric modulator of the glutamatergic system

An optimized synthesis of N-{5-[(1,11-dimethyl-4,8,12-trioxo-3,6,9-triazatricyclo[7.3.1.1^3,11]tetradec-6-yl)methyl]-indan-2-yl}-1,3-benzodioxole-5-carboxamide has been carried out from indan-2-one oxime in seven steps. In vitro studies using electrophysiological patch clamp technique have revealed a positive modulation effect of this compound on kainate induced currents in Purkinje neurons in a wide range of concentrations from 10^–12 to 10^–8 m.     

2-(1,11-十一亚甲基)-5-取代亚氨基-Δ3-1,3,4-噻二唑啉的合成及杀菌活性

通过环十二酮与N-取代氨基硫脲的缩合反应,合成了一系列N-取代环十二酮缩氨基硫脲,经MnO2氧化关环,得到15种未见文献报道的标题化合物,其结构经IR,13C NMR,元素分析的确证. 初步实验表明,部分化合物具有一定的杀菌活性.     

Synthesis, structure, and physical properties of 1,11-o-benzeno[2]orthocyclo[2](1,2)tropyliophane

The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pK_R⁺ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure.     

Theoretical conformational study of the stabilities and geometries of [2,2] (2,7)naphthalenophane-1,11-diene and related compounds

This theoretical study was to determine the relative stability of the different species proposed experimentally and to establish which of the two pathways suggested is the most probable. A conformational study of the geometries of the stable compounds has been carried out using the semiempirical quantum mechanic method AM1 . © 1994 John Wiley & Sons, Inc.     

Regarding the structure of [2.2](2,6,2',7')-naphthalenophane-1,11-diene and its conformational mobility

The synthesis of [2.2](2,6,2',7')naphthalenophane -1,11 - diene 4 has been effected by pyrolysis of the bis-sulphoxide 10, in turn prepared by a ring-contraction procedure of the [3.3]dithiacyclophane 7. The diene 4 has been fully characterized by spectroscopic and chemical methods. The variable-temperature ¹H NMR spectra of the diene 4 indicated that the compound undergoes conformational flipping in solution and has a conformational energy barrier ΔG^≠_25°. 14.9 kcal mol^-1 and a coalescence temperature T_c 38° for the internal protons H_c and H_c' (at 100 MHz). These results differ from those previously recorded. A complete assignment of the pmr spectrum of the cyclophane diene 4 at 270 MHz is presented together with the spectrum of the corresponding saturated [2.2]cyclophane 3.     

Surface films obtained by electrochemical oxidation of 1,11-bis(3-indolizinin-2-ylquinoxalin-2-on-1-yl)-3,6,9-trioxyundecane

Electrochemical oxidation of 1,11-bis(3-indolizinin-2-ylquinoxalin-2-on-1-yl)-3,6,9-trioxyundecane in 0.1 M Et₄NClO₄ in MeCN on a glassy-carbon electrode leads to surface films of two types depending on the film formation mode. Oxidation at controlled first-peak potentials (E _p ¹ = 0.30 V relative to Fc/Fc⁺) or in the range of potentials ?0.60 → +0.40 → ?0.60 V, ?0.60 → +0.40 → ?1.60 → ?0.60 V in the polycycling mode forms a redox-active film that covers the entire surface of the electrode. The quinoxaline fragments of the film are reduced irreversibly in the supporting solution, while the indolizine fragments are reduced reversibly, forming stable radical cation states; the latter are recorded by ESR in the form of a singlet with a variable width (g = 2.0025, ΔH = 0.15?0.5 mT). The oxidized (radical cation) form of the film is conductive, while the neutral film is not. An insulating film is obtained when oxidation is performed under rigid conditions (?0.60 → +1.70 → ?1.70 → ?0.60 V). Both types of film are colored and have nanosized pores (channels), which can play a discriminant role. It is demonstrated (using the discriminant role of pores) that small molecules may be selectively reduced on film-coated electrodes in the presence of bulkier and more reactive substrates.     

Efficient synthesis of <Emphasis Type="Italic">N</Emphasis>-Substituted 1,11-dioxa-4,8-dithia-6-azacyclotridecanes

An efficient procedure has been developed for the synthesis of N-substituted 1,11-dioxa-4,8-dithia-6-azacyclotridecanes by recyclization of 1,6,9-trioxa-3,12-dithiacyclotridecane with substituted anilines and quinolinamines in the presence of Sm(NO₃)₃ · 6 H₂O as catalyst.     

Extraction of rare earth elements with functionalized ionic liquid, 1,11-bis(1-methylimidazol-3-yl)-3,6,9-trioxaundecane bis(hexafluorophosphate)

Interfacial distribution of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y between aqueous solutions of their salts and solutions of functionalized ionic liquid, 1,11-bis(1-methylimidazol-3-yl)-3,6,9-trioxaundecane bis(hexafluorophosphate) has been studied. The stoichiometry of extracted complexes has been determined, the effect of HNO₃ concentration in aqueous phase on the efficiency of rare earth elements(III) recovery into organic phase has been considered.