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1.
Peter Uebelhart Peter Mohler Reza-Ali Fallahpour Hans-Jürgen Hansen 《Helvetica chimica acta》1995,78(6):1437-1464
The dehydrogenation reaction of the heptalene-4,5-dimethanols 4a and 4d , which do not undergo the double-bond-shift (DBS) process at ambient temperature, with basic MnO2 in CH2Cl2 at room temperature, leads to the formation of the corresponding heptaleno[1,2-c]furans 6a and 6d , respectively, as well as to the corresponding heptaleno[1,2-c]furan-3-ones 7a and 7d , respectively (cf. Scheme 2 and 8). The formation of both product types necessarily involves a DBS process (cf. Scheme 7). The dehydrogenation reaction of the DBS isomer of 4a , i.e., 5a , with MnO2 in CH2Cl2 at room temperature results, in addition to 6a and 7a , in the formation of the heptaleno[1,2-c]-furan-1-one 8a and, in small amounts, of the heptalene-4,5-dicarbaldehyde 9a (cf. Scheme 3). The benzo[a]heptalene-6,7-dimethanol 4c with a fixed position of the C?C bonds of the heptalene skeleton, on dehydrogenation with MnO2 in CH2Cl2, gives only the corresponding furanone 11b (Scheme 4). By [2H2]-labelling of the methanol function at C(7), it could be shown that the furanone formation takes place at the stage of the corresponding lactol [3-2H2]- 15b (cf. Scheme 6). Heptalene-1,2-dimethanols 4c and 4e , which are, at room temperature, in thermal equilibrium with their corresponding DBS forms 5c and 5e , respectively, are dehydrogenated by MnO2 in CH2Cl2 to give the corresponding heptaleno[1,2-c]furans 6c and 6e as well as the heptaleno[1,2-c]furan-3-ones 7c and 7e and, again, in small amounts, the heptaleno[1,2-c]furan-1-ones 8c and 8e , respectively (cf. Scheme 8). Therefore, it seems that the heptalene-1,2-dimethanols are responsible for the formation of the furan-1-ones (cf. Scheme 7). The methylenation of the furan-3-ones 7a and 7e with Tebbe's reagent leads to the formation of the 3-methyl-substituted heptaleno[1,2-c]furans 23a and 23e , respectively (cf. Scheme 9). The heptaleno[1,2-c]furans 6a, 6d , and 23a can be resolved into their antipodes on a Chiralcel OD column. The (P)-configuration is assigned to the heptaleno[1,2-c]furans showing a negative Cotton effect at ca. 320 nm in the CD spectrum in hexane (cf. Figs. 3–5 as well as Table 7). The (P)-configuration of (–)- 6a is correlated with the established (P)-configuration of the dimethanol (–)- 5a via dehydrogenation with MnO2. The degree of twisting of the heptalene skeleton of 6 and 23 is determined by the Me-substitution pattern (cf. Table 9). The larger the heptalene gauche torsion angles are, the more hypsochromically shifted is the heptalene absorption band above 300 nm (cf. Table 7 and 8, as well as Figs. 6–9). 相似文献
2.
It is shown that the thermal electrocyclic ring-closure reaction of 1,2-di[(E)-prop-1-enyl]benzene to yield 2,3-dimethylnaphthalene (cf. Scheme 1) [10] can successfully be applied also to the synthesis of benz[a]azulenes (cf. Schemes 2 and 3). Starting materials are methyl 4,6,8-trimethylazulen-2-yl ketone ( 6 ) and the corresponding 2-carbaldehyde 5 , which, in a Horner-Emmons reaction, are transformed into the (azulen-2-yl)-acrylates (E)- 8 and (E)- 7 , respectively. Vilsmeier formylation of these compounds, followed by the Horner-Emmons reaction leads to the formation of the bisacrylates (E,E)- 11 and (E,E)- 12 , respectively. In an alternative reaction, (E)- 8 , on treatment with dimethyl acetylenedicarboxylate (ADM) in the presence of [RuH2(PPh3)4], can be transformed into the methoxycarbonyl-substituted bisacrylates (E,E)- and (E,Z)- 17 . All three bisacrylates, on heating at 180–190° in p-cymene, undergo cyclization to yield the corresponding dihydrobenz[a]azulenes 13 , 14 , and 18 , respectively, which could easily be dehydrogenated on heating in the presence of Pd/C. The new benz[a]azulenes 15 , 16 , and 19 are fully characterized. 相似文献
3.
Ladan Rashidi Ebrahim Vasheghani-Farahani Masoud Soleimani Amir Atashi Khosrow Rostami Fariba Gangi Masoud Fallahpour Mohammad Taher Tahouri 《Journal of nanoparticle research》2014,16(3):1-14
In this study, the effects of intracellular delivery of various concentrations of gallic acid (GA) as a semistable antioxidant, gallic acid-loaded mesoporous silica nanoparticles (MSNs-GA), and cellular uptake of nanoparticles into Caco-2 cells were investigated. MSNs were synthesized and loaded with GA, then characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, N2 adsorption isotherms, X-ray diffraction, and thermal gravimetric analysis. The cytotoxicity of MSNs and MSNs-GA at low and high concentrations were studied by means of 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) test and flow cytometry. MSNs did not show significant toxicity in various concentrations (0–500 μg/ml) on Caco-2 cells. For MSNs-GA, cell viability was reduced as a function of incubation time and different concentrations of nanoparticles. The in vitro GA release from MSNs-GA exhibited the same antitumor properties as free GA on Caco-2 cells. Flow cytometry results confirmed those obtained using MTT assay. TEM and fluorescent microscopy confirmed the internalization of MSNs by Caco-2 cells through nonspecific cellular uptake. MSNs can easily internalize into Caco-2 cells without deleterious effects on cell viability. The cell viability of Caco-2 cells was affected during MSNs-GA uptake. MSNs could be designed as suitable nanocarriers for antioxidants delivery. 相似文献
4.
5.
The methylenation reaction of methyl azulene-2-carboxylates (cf. Schemes 1 and 2) with Tebbe's or Takai's reagent is described. When the prescribed amount of Takai's reagent is applied in a four-fold excess, the corresponding cyclopropyl methyl ethers are formed instead of the enol ethers (cf. Schemes 2 and 3). Similarly, methyl benzoate and methyl 2-naphthoate yield, after treatment with Takai's reagent and hydrolysis, the corresponding cyclopropanols 18 and 19 , respectively (Scheme 3). The cyclopropyl methyl ether 4 or cyclopropanol 5 rearrange, on acid catalysis, into the l-(azulen-2-yl)propan-l-one 20 (Scheme 4). whose reduction with Et3SiH in CF3COOH yields the 2-propylazulene 21 . 相似文献
6.
Sodium [1,3-13C2]cyclopentadienide in tetrahydrofuran (THF) has been prepared from the corresponding labelled [13C2]cyclopentadiene which was synthesized from 13CO2 and (chloromethyl)trimethylsilane (cf. Scheme 10) according to an established procedure. It could be shown that the acetate pyrolysis of cis-cyclopentane-1,2-diyl diacetate (cis- 22 ) at 550 ± 5° under reduced pressure (60 Torr) gives five times as much cyclopentadiene as trans- 22 . The reaction of sodium [1,3-13C2]cyclopentadienide with 2,4,6-trimethylpyrylium tetrafluoroborate in THF leads to the formation of the statistically expected 2:2:1 mixture of 4,6,8-trimethyl[1,3a-13C2], -[2,3a-13C2]-, and -[1,3-13C2]azulene ( 20 ; cf. Scheme 7 and Fig. 1). Formylation and reduction of the 2:2:1 mixture [13C2]- 20 results in the formation of a 1:1:1:1:1 mixture of 1,4,6,8-tetramethyl[1,3-13C2]-, -[1,3a-13C2]-, -[2,3a-13C2]-, -[2,8a-13C2]-, and -[3,8a-13C2]azulene ( 5 ; cf. Scheme 8 and Fig. 2). The measured 2J(13C, 13C) values of [13C2]- 20 and [13C2]- 5 are listed in Tables 1 and 2. Thermal reaction of the 1:1:1:1:1 mixture [13C2]- 5 with the four-fold amount of dimethyl acetylenedicarboxylate (ADM) at 200° in tetralin (cf. Scheme 2) gave 5,6,8,10-tetramethyl-[13C2]heptalene-1,2-dicarboxylate ([13C2]- 6a ; 22%), its double-bond-shifted (DBS) isomer [13C2]- 6b (19%), and the corresponding azulene-1,2-dicarboxylate 7 (18%). The isotopically isomeric mixture of [13C2]- 6a showed no 1J(13C,13C) at C(5) (cf. Fig. 3). This finding is in agreement with the fact that the expected primary tricyclic intermediate [7,11-13C2]- 8 exhibits at 200° in tetralin only cleavage of the C(1)? C(10) bond and formation of a C(7)? C(10) bond (cf. Schemes 6 and 9), but no cleavage of the C(1)? C(11) bond and formation of a C(7)? C(11) bond. The limits of detection of the applied method is ≥96% for the observed process, i.e., [1,3a-13C2]- 5 + ADM→ [7,11-13C2]- 8 →[1,6-13C2]- 9 →[5,10a-13C2]- 6a (cf. Scheme 6). 相似文献
7.
It is shown that the 2-(hydroxymethyl)-1-methylazulenes 6 are being oxidized by activated MnO2 in CH2Cl2 at room temperature to the corresponding azulene-1,2-dicarbaldehydes 7 (Scheme 2). Extension of the MnO2 oxidation reaction to 1-methyl- and/or 3-methyl-substituted azulenes led to the formation of the corresponding azulene-1-carbaldehydes in excellent yields (Scheme 3). The reaction of unsymmetrically substituted 1,3-dimethyl-azulenes (cf. 15 in Scheme 4) with MnO2 shows only little chemoselectivity. However, the observed ratio of the formed constitutionally isometric azulene-1-carbaldehydes is in agreement with the size of the orbital coefficients in the HOMO of the azulenes. The reaction of guaiazulene ( 18 ) with MnO2 in dioxane/H2O at room temperature gave mainly the expected carbaldehyde 19 . However, it was accompanied by the azulene-diones 20 and 21 (Scheme 5). The precursor of the demethylated compound 20 is the carbaldehyde 19 . Similarly, the MnO2 reaction of 7-isopropyl-4-methyalazulene ( 22 ) as well as of 4,6,8-trimethylazulene ( 24 ) led to the formation of a mixture of the corresponding azulene-1,5-diones and azulene-1,7-diones 20 / 23 and 25 / 26 , respectively, in decent yields (Schemes 6 and 7). No MnO2 reaction was observed with 5,7-dimethylazulene. 相似文献
8.
Reza‐Ali Fallahpour Anthony Linden 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(5):o283-o285
In the nearly planar title compound, C15H10IN3, the three pyridine rings exhibit transoid conformations about the interannular C—C bonds. Very weak C—H...N and C—H...I interactions link the molecules into ribbons. Significant π–π stacking between molecules from different ribbons completes a three‐dimensional framework of intermolecular interactions. Four different packing motifs are observed among the known structures of simple 4′‐substituted terpyridines. 相似文献
9.
Fatemah Ayatollah Zadeh Shirazi Amir Fallahpour Mohammad Reza Mardanbeigi & Zahra Nili Ahmadabadi 《分析论及其应用》2022,38(1):110-120
For a finite discrete topological space $X$ with at least two elements, a nonempty set $\Gamma$, and a map $\varphi:\Gamma \to \Gamma$, $\sigma_{\varphi}:X^{\Gamma} \to X^{\Gamma}$with $\sigma_{\varphi}((x_{\alpha})_{\alpha \in \Gamma})=(x_{\varphi(\alpha)})_{\alpha \in \Gamma}$ (for $(x_{\alpha})_{\alpha \in \Gamma} \in X^{\Gamma}$) is a generalized shift. In this text for $\mathcal{S} = \{\sigma_{\varphi}:\varphi \in \Gamma^{\Gamma}\}$ and $\mathcal{H}=\{\sigma_{\varphi}:\Gamma \xrightarrow{\varphi} \Gamma$ is bijective$\}$ we study proximal relations of transformation semigroups $(\mathcal{S}, X^{\Gamma})$ and $(\mathcal{H}, X^{\Gamma})$. Regarding proximal relation we prove: $$P(\mathcal{S}, X^{\Gamma}) = \{((x_{\alpha})_{\alpha \in \Gamma},(y_{\alpha})_{\alpha \in \Gamma}) \in X^{\Gamma} \times X^{\Gamma} : \exists \beta \in \Gamma (x_{\beta} = y_{\beta})\}$$and $P(\mathcal{H}, X^{\Gamma} ) \subseteq \{((x_{\alpha})_{\alpha \in \Gamma},(y_{\alpha})_{\alpha \in \Gamma}) \in X^{\Gamma} \times X^{\Gamma} : \{\beta \in \Gamma : x_{\beta} = y_{\beta}\}$ is infinite$\}$ $\cup\{($ $x,x) : x \in \mathcal{X}\}$. Moreover, for infinite $\Gamma$, both transformation semigroups $(\mathcal{S}, X^{\Gamma})$ and $(\mathcal{H}, X^{\Gamma})$ are regionally proximal, i.e., $Q(\mathcal{S}, X^{\Gamma}) = Q(\mathcal{H}, X^{\Gamma} ) = X^{\Gamma} \times X^{\Gamma}$, also for sydetically proximal relation we have $L(\mathcal{H}, X^{\Gamma}) = \{((x_{\alpha})_{\alpha \in \Gamma},(y_{\alpha})_{\alpha \in \Gamma}) \in X^{\Gamma} \times X^{\Gamma} : \{\gamma ∈ \Gamma :$ $x_{\gamma} \neq y_{\gamma}\}$ is finite$\}$. 相似文献
10.
In this paper, we solve the Schrödinger equation for q-deformed hyperbolic Pöshel-Teller (PT) potential and we obtain the wave function and ladder operators for it. We show that these operators satisfy commutation relations of su(2) Lie algebra. Then we build the generalized coherent states for this q-deformed potential. We show that for the case q=1, we can obtain the same generalized coherent states for usual hyperbolic PT potential. 相似文献