- Tuning the moisture and thermal stability of metal-organic frameworks through incorporation of pendant hydrophobic groups
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An isostructural series of NbO-type porous metal-organic frameworks (MOFs) with different dialkoxy-substituents of formula Cu2(TPTC-OR) (TPTC-OR = 2′,5′-di{alkyl}oxy-[1,1′:4′,1″-terphenyl]-3, 3″,5,5″-tetracarboxylate, R = Me, Et, nPr, nHex) has been synthesized and characterized. The moisture stability of the materials has been evaluated, and a new superhydrophobic porous MOF has been identified. The relationship between pendant side chain length and thermal stability has been analyzed by in situ synchrotron powder X-ray diffraction, showing decreased thermal stability as the side chain length is increased, contradictory to thermogravimetric decomposition studies. Additionally, the four materials exhibit moderate Brunauer-Emmett-Teller (BET) and Langmuir surface areas (1127-1396 m2 g-1 and 1414-1658 m2 g -1) and H2 capacity up to 1.9 wt % at 77 K and 1 bar.
- Makal, Trevor A.,Wang, Xuan,Zhou, Hong-Cai
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Read Online
- Substituted poly(p-phenylene) thin films via Surface-Initiated Kumada-Type catalyst transfer polycondensation
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Conjugated polymer films of unsubstituted and alkoxy-substituted poly(p-phenylene) have been prepared via a Kumada-type catalyst-transfer polycondensation in a grafting-from configuration. A surface-bound external initiator was formed by reacting a Ni(O) complex with a thienyl bromide monolayer, and this surface-bound initiator was used to polymerize several Grignard monomers prepared from the corresponding 1,4-dihalobenzenes resulting in surface-bound, conjugated polymer chains with thickness up to 30 nm. A series of 1,4-diodo monomers with alkoxy side chains ranging from unsubstituted 1,4-diiodobenzene to 1,4-diiodo-2,5-dihexyloxybenzene were polymerized in order to explore the influence of steric bulk on the surface-initiated polymerization process. Within the series of molecules, it was observed that monomers with smaller, less bulky side chains were more easily polymerized from the surface, resulting in smooth, regular films for unsubstituted and methoxy-substituted polyphenylene. Islands of polymer growth were observed with the ethoxy-substituted material and only sparse, irregular growth for the hexyloxysubstituted polymer. The resulting films were characterized by AFM., infrared spectroscopy, ellipsometry, and UV-vis spectroscopy.
- Marshall, Nicholas,Sontag, S. Kyle,Locklin, Jason
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Read Online
- Synthesis of p-Di[1-13C]ethoxybenzene from [1-13C]iodoethane with high labeling efficiency
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p-Di[1-13C]ethoxybenzene was synthesized in high yield and with high labeling efficiency from hydroquinone and [1-13C]iodoethane in the presence of a base in dry acetone. Some p-[1-13C]ethoxyphenol was also formed, from which further p-di[1-13C]ethoxybenzene could be synthesized.
- Iida, Katsumi,Kajiwara, Masahiro
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Read Online
- Light assisted O-alkylation of phenols to ethers using layered double oxides catalyst under green and mild conditions
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O-alkylation of phenols with dialkyl carbonates to ethers over layered double oxides (LDOs) catalyst under light irradiation is described. A base additive is not required when using the longer-chain diethyl carbonate as an alkylating agent owing to the sufficient basicity provided by LDOs. The synergism of substrate phenols molecules absorbing light to reach the first excited states with acid–base pairs of catalyst enhanced the interaction of reactant molecules with the surface of LDOs, simultaneously accelerating the cleavage of phenolic hydroxyl groups. A variety of phenols are tolerated in this system. This work reports a simple and environmentally benign catalytic process for the dehydrogenation of phenolic hydroxyl groups.
- Wang, Ruiyi,Wang, Xiaoyu,Zheng, Zhanfeng
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- Double-triazole substituted ethoxy compound and its preparation method and application
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The invention discloses a double-triazole substituted ethoxy benzene compound and a preparation method and application thereof. The organic compound is prepared by conducting reflux reaction on 1,4-bis (bromomethyl)-2,5-diethoxy benzene with 3-(1H-1,2,4-triazole-1-yl) propionitrile in acetonitrile, and then conducting basic hydrolysis. The preparation method of the present invention has the characteristics of simple operation, low production cost and little environmental pollution, and is applicable to large scale industrialization production. The compound prepared by the invention can be applied to the research on bactericide. The experimental results confirm that the double-triazole substituted ethoxy benzene compound has certain sterilization activity on Escherichia coli and Staphylococcus aureus, especially significant bactericidal activity against Staphylococcus aureus.
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Paragraph 0032-0034
(2017/08/25)
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- Solvent-free synthesis of pillar[6]arenes
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An efficient solvent-free procedure for the synthesis of pillar[6]arenes has been developed. The procedure involves the solid-state condensation of finely milled 1,4-dialkoxybenzene and paraformaldehyde by grinding in the presence of a catalytic amount of H2SO4. The use of organic solvents for the extraction of products has also been avoided. Operational simplicity, compatibility with various 1,4-dialkoxybenzenes, non-chromatographic purification technique, high yields and mild reaction conditions are the notable advantages of this procedure. A large scale reaction demonstrated the practical applicability of this methodology.
- Santra,Kopchuk,Kovalev,Zyryanov,Majee,Charushin,Chupakhin
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supporting information
p. 423 - 426
(2016/01/30)
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- Practical Ligand-Free Copper-Catalysed Short-Chain Alkoxylation of Unactivated Aryl Bromides
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An efficient and practical short-chain alkoxylation of unactivated aryl bromides has been developed with special attention focussed on the applicability of the reaction. Sodium alkoxide is used as the nucleophile, and the corresponding alcohol as the solvent. The reaction requires neither precious metals nor organic ligands. It uses a catalytic system consisting of copper(I) bromide as a catalyst, the corresponding alkyl formate as a noncontaminating cocatalyst, and lithium chloride as an additive. A wide range of substrates and test cases highlight the synthetic utility of the approach. Considering the commercial accessibility and affordability of the feedstocks, this protocol shows promise as a new alternative for the sustainable preparation of aryl alkyl ethers.
- Guo, Ying,Fan, Xue-Min,Nie, Min,Liu, Hong-Wei,Liao, Dao-Hua,Pan, Xian-Dao,Ji, Ya-Fei
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p. 4744 - 4755
(2015/08/03)
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- Synthesis and surfactochromicity of 1,4-diketopyrrolo[3,4-c]pyrrole(DPP)- based anionic conjugated polyelectrolytes
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Two novel anionic conjugated copolyelectrolytes PSDPPPV and PSDPPPE were synthesized via Heck/Sonogashira coupling reactions and characterized by FT-IR, 1H NMR, UV-vis, and PL spectroscopy. The two polymers are respectively constituted of 2,5-diethoxy-1,4-phenyleneethynylene (DPV) and 2,5-diethoxy-1,4-phenyleneethynylene (DPE) with 1,4-diketo-2,5-bis(4- sulfonylbutyl)-3,6-diphenylpyrrolo[3,4-c]pyrrole (SDPP) which is a novel water soluble diketopyrrolopyrrole derivative. PSDPPPV and PSDPPPE show broad absorption band in visible region and they exhibit strong fluorescence quenching in aqueous solution. The fluorescence of their aqueous solutions can be enhanced in the presence of cationic surfactant or polymer nonionic surfactant. Fluorescence enhancement by introduction of polyvinylpyrrolidone (PVP) shows linear response. This result provides a controllable method to increase fluorescence intensity of dipyrrolopyrrole-based conjugate polyelectrolytes in aqueous phase. The optical properties suggested that PSDPPPV and PSDPPPE which are negatively charged conjugated polymers can assemble with positively charged photovoltaic materials to form ionic photoactive layer.
- Shen, Haoyue,Kou, Chun,He, Min,Yang, Han,Liu, Kuan
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p. 739 - 751
(2014/03/21)
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- SNAAP sulfonimidate alkylating agent for acids, alcohols, and phenols 1
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Stable, crystalline ethyl N-tert-butyl-4-nitrobenzenesulfonimidate has been prepared in high yield by direct O-ethylation of N-tert-butyl-4- nitrobenzenesulfonamide with iodoethane and silver(I) oxide in dichloromethane. This sulfonimidate directly ethylates various acids to esters; the stronger the acid, the faster it alkylates and in higher yield. It readily ethylates alcohols and phenols to ethers at room temperature in the presence of tetrafluoroboric acid catalyst without molecular rearrangements or racemization. We have defined these reactions as SNAAP alkylations: [substitution, nucleophilic of acids, alcohols and phenols]. The hard sulfonimidate alkylating agent is chemoselective, preferring oxygen > nitrogen > sulfur. The sulfonamide byproduct of alkylation is readily recycled to the sulfonimidate. Georg Thieme Verlag Stuttgart . New York.
- Maricich, Tom J.,Allan, Matthew J.,Kislin, Brett S.,Chen, Andrea I-T.,Meng, Fan-Chun,Bradford, Christine,Kuan, Nai-Chia,Wood, Jeremy,Aisagbonhi, Omonigho,Poste, Alethea,Wride, Dustin,Kim, Sylvia,Santos, Therese,Fimbres, Michael,Choi, Dianne,Elia, Haydi,Kaladjian, Joseph,Abou-Zahr, Ali,Mejia, Arturo
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p. 3361 - 3368
(2014/01/06)
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- Copper(II) ion-sensing mechanism of oligo-phenylene vinylene derivatives: Syntheses and theoretical calculations
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Oligo-phenylene vinylene (oligo-PV) with two picolinamide side-groups and six methoxy end-groups was synthesized in order to be a fluorescent sensing molecule. Various metal ion solutions (1.5×10-4 M) were added to the 1.5×10-6 M acetonitrile solution of the fluorescent molecule. The fluorescent emission spectra showed that, at about the same concentration (1.5×10-4 M), only Cu(II) ion can quench the fluorescent emission of the picolinamide-PV solution. Possible metal ion-sensing mechanisms could be either the binding at picolinamide side-groups or methoxy end-groups, or interchain-stacking driven by the metal ions. Hence, oligo-PVs with six methoxy end-groups but without substituted side-groups, and another oligo-PV with six methoxy end-groups and two ethoxy side-groups were synthesized for comparison. These molecules turned out to be inactive to any metal ion solutions. Moreover, quantum calculation was used to confirm the result. Binding energy and conformation were calculated and simulated. It could be concluded that nitrogen and oxygen atoms of the picolinamide group and one oxygen atom from the methoxy group are involved in the metal ion-binding process.
- Tongkate, Pratoomrat,Phromyothin, Darinee,Sumranjit, Jitapa
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experimental part
p. 3329 - 3335
(2012/07/03)
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- METHODS AND COMPOSITIONS FOR CONTROL OF GYPSY MOTHS, Lymanria dispar
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The invention provides in part dialkoxybenzene and eugenol compounds for controlling infestation by a Lymantria dispar, and methods thereof. The compounds include a compound of Formula I: where R1 may be methyl, ethyl, propyl, n-butyl, isopentyl (3-methylbutyl) or allyl; R2 may be at positions 2, 3 or 4 and may be H, methyl, ethyl, propyl, n-butyl, isopentyl (3-methylbutyl) or allyl; and R3 may be optionally present at positions 2, 3 and 4, and is allyl; with the provisos that when R2 is at position 2, R3 if present is at position 3, or when R2 is at to position 3, R3 if present is at positions 2 or 4, or when R2 is at position 4, R3 if present is at position 2; or of Formula II: where R1 may be methyl, ethyl, propyl, n-butyl, isopentyl (3-methylbutyl) or allyl; or mixtures thereof.
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Page/Page column 11
(2010/08/07)
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- METHODS AND COMPOSITIONS FOR CONTROL OF CABBAGE LOOPER, Trichoplusia ni
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The invention provides in part dialkoxybenzene compounds for controlling infestation by a Trichoplusia ni, and methods thereof. The compounds include a compound of Formula I: where R1 may be methyl, ethyl, propyl, n-butyl, isopentyl(3-methylbutyl) or allyl; R2 may be at positions 2, 3 or 4 and may be H, methyl, ethyl, propyl, n-butyl, isopentyl(3-methylbutyl) or allyl; and R3 may be optionally present at positions 2, 3 and 4, and is allyl; except that when R2 is at position 2, R3 if present is at position 3, and when R2 is at position 3, R3 if present is at positions 2 or 4, and when R2 is at position 4, R3 if present is at position 2, and when R2 is at position 4 and R3, if present, has reacted with an OH group at position 1 in a Markovnikov sense, then R3 becomes R4, a dihydrofuran.
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Page/Page column 11
(2010/07/04)
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- UV-vis absorption spectra of 1,4-dialkoxy-2,5-bis[2-(thien-2-yl)ethenyl]benzenes
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Complex theoretical and experimental studies and quantum-chemical calculations were applied to study the UV-vis spectroscopic features of the novel compounds: three stereoisomers of 1,4-diethoxy-2,5-bis[2-(5-methylthien-2-yl)ethenyl]benzene (A-C) and E,E isomer of 1,4-diisopropoxy-2,5-bis[2-(thien-2-yl)ethenyl]benzene (D). These structures are the derivatives of 2,5-bis[2-(thien-2-yl)ethenyl]benzene, and belong to a group of thienyl-PPV family that are able to polymerize due to the presence of π-conjugated bonding system. It was established that such compounds during electropolymerization are strongly dependent on their stereochemistry and on the eventual presence of substituents in α-positions of the tiophene ring. We have obtained a good agreement between the theoretically simulated optical within a framework of TDDFT approach and experimentally measured data. Influence of PMMA polymer matrices on the UV-vis spectra is explored. It is shown that a red wavelength spectral shift is observed only for D compounds and agreement between calculated and experimental spectral data is sufficiently good. This may indicate on different influence of local polymer matrix field on the spectral behaviors of the chromophores with different stereochemistry.
- Fuks-Janczarek,Reshak, Ali H.,Kuznik,Kityk,Gabanski,Lapkowski,Motyka,Suwinski
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experimental part
p. 394 - 398
(2009/04/13)
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- Screening of dialkoxybenzenes and disubstituted cyclopentene derivatives against the cabbage looper, Trichoplusia ni, for the discovery of new feeding and oviposition deterrents
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The antifeedant, oviposition deterrent, and toxic effects of dialkoxybenzene minilibraries and of disubstituted cyclopentene minilibraries (i.e., consisting of four to five compounds) along with their pure constituent compounds were assessed against third instar larvae and adults of the cabbage looper, Trichoplusia ni, in laboratory bioassays in a search for new insect control agents. These compounds mimic naturally occurring bioactive odorants and tastants and are relatively easily prepared from commodity chemicals. Most of these libraries strongly deterred larval feeding, with some exhibiting strong toxic and oviposition deterrent effects as well. Our results suggest some structure-function relationships within these libraries. Replacement of a methyl group with larger alkyl substituents increased the feeding deterrent effects in most cases. The presence of a free hydroxyl group, irrespective of the carbon framework or alkyl substituent, served to reduce feeding deterrent effects in all series of compounds. Further, exceeding a certain group size also generally had a detrimental effect. This information will be useful in designing new insect control agents for agriculture. Some of these libraries and compounds may have potential for development as commercial insecticides.
- Akhtar, Yasmin,Isman, Murray B.,Paduraru, Peggy M.,Nagabandi, Srinivas,Nair, Ranjeet,Plettner, Erika
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scheme or table
p. 10323 - 10330
(2009/10/02)
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- The synthesis and conformation of oxygenated trianglimine macrocycles
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The synthesis of series of D2h and C2v symmetric oxygenated aromatic dicarboxaldehydes, using dilithiation methodology, is described along with their reactivity in the [3 + 3] cyclocondensation reaction with (1R,2R)-diaminocyclohexane to give oxygenated trianglimine macrocycles. Macrocycles derived from C2v symmetric dialdehydes give macrocycles with a stereogenic aromatic plane with complete diastereocontrol, as a mixture of retainers.
- Kuhnert, Nikolai,Lopez-Periago, Ana,Rossignolo, Giulia M.
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p. 524 - 537
(2007/10/03)
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- Alkoxylated p-phenylenevinylene oligomers: Synthesis and spectroscopic and electrochemical properties
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Twenty-one n-alkoxy substituted phenylenevinylene oligomers were synthesized, varying in size, number and position of the OR groups. IR,MS and solubility data are presented. NMR measurements provided the molecular structure as well as information about conformations and molecular dynamics. UV and of cyclic voltammetric data give correlations of chemical structure (number and position of OR substituents) with separate HOMO and LUMO energies.
- Ndayikengurukiye, Henri,Jacobs, Sven,Tachelet, Wim,Van Der Looy, Johan,Pollaris, Anne,Geise, Herman J.,Claeys, Magda,Kauffmann, Jean M.,Janietz, Silvia
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p. 13811 - 13828
(2007/10/03)
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- Phase transfer catalysis without solvent. Alkylation of phenol and derivatives
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The alkylation of phenol, hydroquinone and p-aminophenol is performed by phase transfer catalysis without solvent. High yields of α,ω-diphenoxyalkanes, hydroquinone diethers and high selective mono O-alkylation of p-aminophenol are obtained in very mild conditions.
- Loupy,Sansoulet,Diez-Barra,Carrillo
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p. 1465 - 1471
(2007/10/02)
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- The Electrochemical Metoxylation of Dialkoxyaromatic Compounds and the Determination of Isomer Ratios by N.M.R. Spectroscopy
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Electrolysis in methanol-KOH solution of p-diethoxy-, p-di-n-propoxy-, p-di-isopropoxy-, p-di-n-butoxy-, p-di-isobutoxy-, and p-di-s-butoxy-benzenes afforded the corresponding 3,6-dialkoxy-3,6-dimethoxy-cyclohexa-1,4-diene, shown by 1H n.m.r. spectroscopy to be an approximately equimolar mixture of cis- and trans-isomers.Likewise, from 9,10-diethoxyanthracene was obtained an equimolar mixture of the cis- and trans-isomers of 9,10-diethoxy-9,10-dimethoxy-9,10-dihydroanthracene.
- Elgy, Geraldine M.,Jennings, W. Brian,Pedler, Alan E.
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p. 1255 - 1260
(2007/10/02)
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