- Reaction of Hydroxymethyl- and Alkyl-Substituted Azulenes with Manganese Dioxide
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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-methy
- Fallahpour, Reza-Ali,Sigrist, Rolf,Hansen, Hans-Juergen
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- Synthesis and characterisation of long wavelength-absorbing donor/acceptor-substituted methine dyes
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By the reaction of aromatic or heteroaromatic formyl compounds or their corresponding iminium salts with active methylene compounds a series of new methine dyes with long-wavelength absorption in the near-infrared spectral range were prepared.
- Heichert, Christoph,Hartmann, Horst
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- Photophysical, electrochemical, and photoelectrochemical properties of new azulene-based dye molecules
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Four new azulene-based dye molecules, 3-(azulen-1-yl)-2-cyanoacrylic acid (Azu-1), 3-(7-isopropyl-1,4-dimethylazulen-3-yl)-2-cyanoacrylic acid (Guai-1), 5-(azulen-1-yl)-2-cyanopenta-2,4-dienoic acid (Azu-2), and 5-(7-isopropyl-1,4- dimethylazulen-3-yl)-2-cyanopenta-2,4-dienoic acid (Guai-2), were synthesized and their photoelectrochemical properties were studied in dye-sensitized solar cells (DSSCs). All of them exhibit, in the visible region, a strong absorption band coming from the S0-S2 transition and a very weak band coming from the S0-S1 transition, and the transition assignments are supported by theoretical calculations using time-dependent density functional theory (TD-DFT) at the B3LYP/6-31G* level. In sensitization of nanocrystalline TiO2 electrodes, reducing their adsorption amount on the TiO2 surface (by co-adsorption with deoxycholic acid) mitigates dye aggregation and improves their photoelectric conversion efficiency greatly. Also, extending the conjugated side chain (Azu-2 vs. Azu-1 or Guai-2 vs. Guai-1) not only shifts their photoelectric response to longer wavelengths and therefore enhances the short-circuit photocurrent, but also increases the open-circuit photovoltage significantly. Moreover, it was found that the electron injection efficiencies varied remarkably with excitation wavelength, suggesting direct electron injection from the S2 state of these dye molecules. The Royal Society of Chemistry.
- Zhang, Xue-Hua,Li, Chao,Wang, Wei-Bo,Cheng, Xue-Xin,Wang, Xue-Song,Zhang, Bao-Wen
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- Stimuli-responsive cyclopenta[ef]heptalenes: Synthesis and optical properties
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We report the one-pot synthesis, 1D and 2D NMR characterization, and UV/Vis study of a series of cyclopenta[ef]heptalenes 4a-c that exhibit strong stimuli-responsive behavior, with a tunable energy gap as a result of perturbation of HOMO, LUMO, and LUMO+1 energies upon doping/dedoping with TFA/Et3N. The approach employed allows for the extension of conjugation at C-4 of the cyclopenta[ef]heptalene skeleton from X = H (4a) to X = CN (4b) and X = 2-thiophenyl (4c), resulting in longer absorption maxima and smaller optical energy gaps of the cyclopenta[ef]heptalenium cations 4a-c+. Additionally, in the presence of a UV-activated ( 300 nm) photoacid generator (PAG), protonation of 4c can be indirectly achieved by intermolecular photoinduced electron transfer (PeT) from the excited state of 4c to the PAG, upon which the latter undergoes photodecomposition resulting in the generation of acid. This phenomenon facilitates the use of cyclopenta[ef]heptalenes 4a-c as visible sensitizers of commercial PAGs.
- Ghazvini Zadeh, Ebrahim H.,Woodward, Adam W.,Richardson, David,Bondar, Mykhailo. V.,Belfield, Kevin D.
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- Thermal Reactions of Guaiazulene and Its 3-Methyl Derivative with Dimethyl Acetylenedicarboxylate
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The thermal reaction of 7-isopropyl-1,3,4-trimethylazulene (3-methylguaiazulene; 2) with excess dimethyl acetylenedicarboxylate (ADM) in decalin at 200 deg C leads to the formation of the corresponding heptalene- (5a/5b and 6a/6b; cf.Scheme 3) and azulene-1,2-dicarboxylates (7 and 8, respectively).Together with small amounts of a corresponding tetracyclic compound ("anti"-13) these compounds are obtained via rearrangement (-> 5a/5b and 6a/6b), retro-Diels-Alder reaction (-> 7 and 8), and Diels-Alder reaction with ADM (-> "anti"-13) from the two primary tricyclic intermediates (14 and 15; cf.Scheme 5) which are formed by site-selective addition of ADM to the five-membered ring of 2.In a competing Diels-Alder reaction, ADM is also added to the seven-membered ring of 2, leading to the formation of the tricyclic compounds 9 and 10 and of the Diels-Alder adducts "anti"-11 and "anti"-12, respectively of 9 and of a third tricyclic intermediate 16 which is at 200 deg C in thermal equilibrium with 9 and 10 (cf.Scheme 6).The heptalenedicarboxylates 5a and 5b as well as 6a and 6b are interconverting slowly already at ambient temperature (Scheme 4).The thermal reaction of guaiazulene (1) with excess ADM in decalin at 190 deg C leads alongside with the known heptalene-(3a) and azulene-1,2-dicarboxylates (4; cf.Schemes 2 and 7) to the formation of six tetracyclic compounds "anti"-17 to "anti"-21 as well as "syn"-19 and small amounts of a 4:1 mixture of the tricyclic carboxylates 22 and 23.The structure of the tetracyclic compounds can be traced back by a retro-Diels-Alder reaction to the corresponding structures of tricyclic compounds (24-29; cf.Scheme 8) which are thermally interconverting by -C shifts at 190 deg C.The tricyclic tetracarboxylates 22 and 23, which are slowly equilibrating already at ambient temperature, are formed by thermal addition of ADM to the seven-membered ring of dimethyl 5-isopropyl-3,8-dimethylazulene-1,2-dicarboxylate (7; cf.Scheme 10).Azulene 7 which is electronically deactivated by the two MeOCO groups at C(1) and C(2) shows no more thermal reactivity in the presence of ADM at the five-membered ring (cf.Scheme 11).The tricyclic tetracarboxylates 32, "anti"-33, and "anti"-34 (cf.Schemes 10-12 as well as Scheme 13).A structural correlation of the tri- and tetracarboxylates (22, 23, and 35-38; cf.Scheme 13) is assumed.The tetracyclic hexacarboxylates, 32, "anti"-33, and "anti'-34 seem to arise from the most strained tricyclic intermediates (36-38) by the Diels-Alder reaction with ADM.
- Uebelhart, Peter,Hansen, Hans-Juergen
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- Method for preparing guaiazulene aldehyde dimer from guaiazulene in two steps
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The invention relates to a method for preparing a guaiazulene aldehyde dimer from guaiazulene in two steps. The method comprises the following steps: 1) synthesis of guaiazulene aldehyde: reacting guaiazulene with DMF and phosphorus oxychloride under anhydrous and anaerobic conditions for 9 hours, evaporating the reaction solution to dryness, extracting with dichloromethane, combining organic phases, and carrying out column chromatography to obtain guaiazulene aldehyde; and 2) synthesis of the guaiazulene aldehyde dimer: dissolving guaiazulene aldehyde in dry toluene, adding a catalytic amountof piperidine and glacial acetic acid, carrying out a reaction at 60 DEG C for 30 hours, evaporating the reaction solution to neutralize glacial acetic acid, extracting dichloromethane, and carryingout column chromatography to obtain the guaiazulene aldehyde dimer. The synthesis process provided by the invention has the advantages of simple steps, mild reaction conditions and higher yield.
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Paragraph 0018; 0024-0026; 0029-0031
(2020/10/14)
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- Preparation and application of guaifenazulene aldole dicondensate (by machine translation)
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The invention belongs to the field, and particularly relates to chemical preparation and application. When the problem group is subjected to chemical synthesis research on the skeleton by guaiguazulene and piperidine acid as raw materials, the derivative trans - 1, 2 - (1, 4 - diazulyl) ethene ene derivative of guaiabazulene is found. H1N1 Influenza virus testing, indicating that the compound is level, 25 mm in vitro antiviral activity superior to that of positive drug ribavirin. In vivo activity tests prove, the compound not only can inhibit the pneumonia symptoms, but also can reduce the titer, and the survival rate. , The survival rate, 5 mg/kg/day the lung virus titer . of virus-infected mice can be remarkably improved when stomach tube-like dosages are used for gastric lavage. In general, the activity of the compound is comparable, and the activity of the compound is comparable to that of oseltamivir. The utility model can be used for preparing antiviral drugs. The invention opens up a new way for deep research and development of new antiviral drugs, which is a new approach. (by machine translation)
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Paragraph 0017; 0018
(2019/08/02)
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- Synthesis and application of novel s-guaiazulene sesquiterpenoid alkaloids
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The invention belongs to the field of synthetic pharmacochemistry and particularly relates to chemical synthesis and an application of a new framework of s-guaiazulene sesquiterpenoid alkaloids from Muriceides collaris. Muriceidine A is successfully designed and synthesized from s-guaiazulene and piperidine acid as raw materials with a chemical method. In order to verify the universality of the synthesis method, azulene aldehyde is linked with piperidine, methylpiperidine, pyrrole, piperidinemethanol, 4-hydroxypiperidine and other N-heterocycle fragments. Screening of antitumor activity in vitro finds that the IC50 values of structure optimized products 2 and 3 for 14 tumor cell strains including 231, MCF-7, K562, HCT-116, Hela, A549, H1975, HUVEC, MGC-803, SH-SY5Y, HO8910, Siha, PC-3 andBEL7402 are smaller than 10 mu M, and therefore, the new framework of s-guaiazulene sesquiterpenoid alkaloids can be used for research and development of antitumor drugs.
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Paragraph 0062-0064
(2019/08/06)
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- Novel cyclometallated 5-π-delocalized donor-1,3-di(2-pyridyl)benzene platinum(ii) complexes with good second-order nonlinear optical properties
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Five new platinum(ii) complexes bearing a cyclometallated 5-π-delocalized donor-1,3-di(2-pyridyl)benzene were prepared and fully characterized. Their second-order nonlinear optical (NLO) properties were determined by the Electric-Field Induced Second Harm
- Fontani, Mattia,Garoni, Eleonora,Colombo, Alessia,Dragonetti, Claudia,Fantacci, Simona,Doucet, Henri,Soulé, Jean-Fran?ois,Boixel, Julien,Guerchais, Véronique,Roberto, Dominique
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supporting information
p. 202 - 208
(2019/01/04)
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- NOVEL AZULENYL COMPOUND
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PROBLEM TO BE SOLVED: To provide: a method for determining amino acid sequences such as trace peptides and proteins; as well as a compound that can be used as an Edman reagent suitable for said method, specifically a compound that has a high UV absorbance and efficiently reacts with peptides. SOLUTION: Provided is an azulenyl isothiocyanate compound represented by the formula (1). (Each R independently is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group or heteroaryl group having 6 to 10 carbon atoms; n is an integer from 0 to 7; in particular, R preferably is an alkyl group having 1 to 10 carbon atoms, and further preferably has substituent group at 1 or more of the carbon 3-, 5-, 8-position.). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0052-0054
(2017/09/20)
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- Preparation, crystal structure, and spectroscopic, chemical, and electrochemical properties of (2E,4E)-1-(3-Guaiazulenyl)-4-(2-thienyl)-1,3- butadiene
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Wittig reaction of (E)-2-(2-thienyl)ethylene-1-carbaldehyde with [(3-guaiazulenyl)methyl]triphenylphosphonium bromide in ethanol containing sodium ethoxide (=NaOC2H5) at 25°C for 24 h under argon gives the two (2E,4E)- and (2E,4Z)-geometric isomers of a new compound 1-(3-guaiazulenyl)-4-(2-thienyl)-1,3-butadiene, the only title (2E,4E)- form, of which can be isolated as single crystals. Preparation, chemical and spectroscopic properties, crystal structure, and electrochemical behavior of the target (2E,4E)-form, compared with those of (E)-1-(3-guaiazulenyl)-2-(2- thienyl)ethylene and the structurally related new compound (3-guaiazulenyl)[(E)- 2-(2-thienyl)ethenyl]methylium hexafluorophosphate, are documented.
- Takekuma, Shin-Ichi,Kobayashi, Norihito,Minematsu, Toshie,Takekuma, Hideko
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p. 968 - 982
(2013/09/12)
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- Preparation, crystal structure, and spectroscopic, chemical, and electrochemical properties of (2E,4E)-1,4-di(3-guaiazulenyl)-1,3-butadiene compared with those of (E)-1,2-di(3-guaiazulenyl)ethylene
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Wittig reaction of (E)-3-(3-guaiazulenyl)propenal (11) with (3-guaiazulenylmethyl)triphenylphosphonium bromide (9) in ethanol containing NaOEt at 25 °C for 24 h under argon gives the title new (2E,4E)-1,3- butadiene derivative 4, in 33% isolated yield, which upon treatment with hexafluorophosphoric acid (i.e., 65% HPF6 aqueous solution) in tetrahydrofuran (=THF) at 25 °C for 1 h under aerobic conditions affords a new air (two-electron) oxidation product (E)-ethylene-1,2-bis(3- guaiazulenylmethylium) bis(hexafluorophosphate) (14), quantitatively, and further, zinc-reduction of 14 in trifluoroacetic acid (=CF3COOH) at 0 °C for 1 h under argon reverts 4, quantitatively. Along with the above interesting results, our discovered another preparation method, spectroscopic properties, crystal structure, and electrochemical behavior of 4, which serves as a strong two-electron donor and acceptor, compared with those of the previously reported (E)-1,2-di(3-guaiazulenyl)ethylene (3) are documented in detail. The title new (2E,4E)-1,3-butadiene derivative 4 serves as a strong two-electron donor. Therefore, the π-electron system 4 is readily converted into a new air (two-electron) oxidation product 14, quantitatively, the reaction conditions, of which are shown in the following scheme. Furthermore, the Zn-reduction of 14 in CF3COOH at 0 °C for 1 h under argon reverts 4, quantitatively. The title unique studies, with several interesting properties of 4 and 14, are reported.
- Takekuma, Shin-Ichi,Yamamoto, Manami,Nakagawa, Aki,Iwata, Tomohiro,Minematsu, Toshie,Takekuma, Hideko
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scheme or table
p. 8318 - 8329
(2012/09/25)
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- Preparation, crystal structure, and spectroscopic, chemical, and electrochemical properties of (2E,4E)-4-[4-(dimethylamino)phenyl]-1-(3-guaiazulenyl)-1,3-butadiene compared with those of (E)-2-[4-(dimethylamino)phenyl]-1-(3-guaiazulenyl)ethylene
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Wittig reaction of 3-[4-(dimethylamino)phenyl]propanal (5) with (3-guaiazulenylmethyl)triphenylphosphonium bromide (4) in ethanol containing NaOEt at 25 °C for 24 h under argon gives the title (2E,4E)-1,3-butadiene derivative 6E in 19% isolated yield. Spe
- Takekuma, Shin-ichi,Matsuoka, Hiroto,Minematsu, Toshie,Takekuma, Hideko
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experimental part
p. 3004 - 3015
(2010/06/14)
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- Preparation, crystal structures, and properties of new conjugated π-electron systems with 3-guaiazulenyl and 4-(dimethylamino)phenyl groups
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Reaction of guaiazulene with l,2-bis[4-(dimethylamino)phenyl]-l,2- ethanediol in methanol in the presence of hydrochloric acid at 60°C for 3h gives l,l-bis[4-(dimethylamino)phenyl]-2-(3-guaiazulenyl)ethylene, in 81% yield, via pinacol rearrangement and fu
- Takekuma, Shin-Ichi,Hori, Seiki,Minematsu, Toshie,Takekuma, Hideko
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body text
p. 1472 - 1484
(2009/05/06)
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- Synthesis, spectroscopy, and reactivity of meso-unsubstituted azuliporphyrins and their heteroanalogues. Oxidative ring contractions to carba-, oxacarba-, thiacarba-, and selenacarbaporphyrins
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This paper reports the first detailed study on meso-unsubstituted azuliporphyrins, an important family of porphyrin-like molecules where one of the usual pyrrole rings has been replaced by an azulene subunit. Although the azulene moiety introduces an elem
- Lash, Timothy D.,Colby, Denise A.,Graham, Shelley R.,Chaney, Sun T.
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p. 8851 - 8864
(2007/10/03)
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- Oxidation of 4,6,8-Trimethylazulene and Guaiazulene with Hydrogen Peroxide in Pyridine
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Oxidation of 4,6,8-trimethylazulene (1) with hydrogen peroxide in pyridine at 25 deg C for 18 h gave 4,6,8-trimethyl-1,5- and -1,7-azulenequinones, their 2-(4,6,8-trimethyl-1-azulenyl) derivatives, and 2,3-dihydro-4,6- and -4,7-dimethyl-2-(4,6,8-trimethyl-1-azulenyl)-1H-inden-1-ones in much higher yields than those by autoxidation of 1 in DMF at 120 deg C.The same oxidation of guaiazulene afforded sixteen separable products, among which there were three new dimeric condensates.
- Matsubara, Yoshiharu,Morita, Masanori,Takekuma, Shin-ichi,Nakano, Tomohiro,Yamamoto, Hiroshi,Nozoe, Tetsuo
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p. 3497 - 3499
(2007/10/02)
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- Autoxidation of Guaiazulene and 4,6,8-Trimethylazulene in Polar Aprotic Solvent: Structural Proof for Products
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Autoxidation of guaiazulene and 4,5,8-trimethylazulene at 100 - 120 deg C in DMF (or HMPA) respectively yielded 25 and 17 separable products, including several known compounds.Most of these new compounds were derivatives of 1,5- and 1,7-azulenequionone, 1H-inden-1-one, naphthoquinone, and benzenoid, or dimeric and trimeric forms; structures of these products were established on the basis of spectroscopic (NMR, UV, IR, and MS) and half-wave potential (E1/2) data. 1H NMR (200-MHz) parameters of various azulene derivatives are given for comparative study.Possible reaction pathways are suggested for the formation of such a wide variety of interesting products.
- Matsubara, Yoshiharu,Takekuma, Shin-ichi,Yokoi, Katsumi,Yamamoto, Hiroshi,Nozoe, Tetsuo
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p. 1415 - 1428
(2007/10/02)
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- 6-(3-Guaiazulenyl)-5-isopropyl-3,8-dimethyl-1(6H)-azulenone and Its Norcaradiene-Isomer. Key Intermediates for Novel Intermolecular One-Carbon Transfer in Autoxidation of Guaiazulene
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Autoxidation of guaiazulene either at 85 deg C in N,N-dimethylformamide-0.5 M sulfuric acid or at 25-35 deg C on the surface of a filter paper yielded, together with other products, the two title compounds which were shown to be in equilibrium and to constitute important intermediates for the intermolecular one-carbon transfer reactions frequently observed during autoxidation of many azulenic hydrocarbons.
- Matsubara, Yoshiharu,Takekuma, Shin-ichi,Yamamoto, Hiroshi,Nozoe, Tetsuo
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p. 455 - 458
(2007/10/02)
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- OXIDATION OF AZULENE DERIVATIVES. AUTOXIDATION OF GUAIAZULENE IN A POLAR APROTIC SOLVENT
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Autoxidation of guaiazulene at 100 deg C in N,N-dimethylformamide afforded twenty-three separable products including seven known compounds.Most of these new compounds possess highly interesting structures of azulenoquinone, inden-1-one, benzocyclobutadien
- Nozoe, Tetsuo,Takekuma, Shin-ichi,Doi, Masashi,Matsubara, Yoshiharu,Yamamoto, Hiroshi
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p. 627 - 630
(2007/10/02)
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