Synthesis of 5-acetyl derivatives of alkyl 2-furoates and 3-(2-furyl)acrylates

Methyl 5-acetyl-2-furoate has been prepared via oxidation of 5-(1-hydroxyethyl)-2-furoate with the Jones reagent. In turn, the starting compound has been synthesized via sequential chloroethylation of ethyl 2-furoate, substitution of chlorine with acetoxy group, and methanolysis of the acetate in presence of sodium methylate. The vinylog 2-furoate has been obtained as the major product via acetylation of ethyl 3-(2-furyl)-acrylate with acetic anhydride in the presence of magnesium perchlorate.

     

Thermal unimolecular decomposition of ethyl 2-furoate and its reactivity toward OH radicals: A theoretical study

Mechanism and kinetics of the thermal pyrolysis of ethyl 2-furoate were studied in a wide range of conditions (ie, 500-1500 K and 1-7600 Torr) using the accurate dual-level theory CCSD(T)&MP2(FC)//B3LYP/aug-cc-pVTZ and state-of-the-art Rice-Ramsperger-Kassel-Marcus based master equation rate model including hindered internal rotation and tunneling treatments. The predicted rate coefficients are found to be in accordance with the experimental data. The mechanism details are revealed as (i) the major decomposition channel occurs via a six-center transition state with the barrier energy of 48.3 kcal/mol at 0 K, leading to the formation of C₂H₄ and 2-furoic acid and (ii) pressure has a slightly positive effect on the rate constant, particularly at the high temperature. Also, the reactivity of ethyl 2-furoate toward OH radicals was discussed in the first place.     

Synthesis of ethyl 4,5-bis(diethoxyphosphorylmethyl)-3-furoate

Preparative procedure for 4,5-bis(diethoxyphosphorylmethyl)-3-furoate from 4-chloromethyl-3-furoate is developed. It includes substitution of chlorine with iodine, phosphorylation by means of the Arbuzov reaction, chloromethylation of 4-(diethoxyphosphorylmethyl)-3-furoate in the position 5 of the furan ring, substitution of chlorine with iodine in the obtained chloromethyl derivative, and repeated phosphorylation with triethyl phosphite. It was found that ethyl 4-(diethoxyphosphorylmethyl)-5(chloromethyl)-3-furoate reacts with sodium diethyl phosphite by two pathways. Besides usual nucleophilic substitution leading to phosphonate, transfer of the reaction center in the position 2 of the furan ring takes place. The ambident diethylphosphite anion in this case reacts at the oxygen to give tertiary phosphite. The latter is oxidized with the air oxygen to form ethyl 2-(diethoxyphosphoryloxy)-4-(diethoxyphosphorylmethyl)-5-methyl-3-furoate. Unlike that analogous iodomethyl phosphonate is phosphorylated selectively under the conditions of the Arbuzov reaction.     

Structure and Kinetics of Desolvation of 2-Hexanone Inclusion Compounds of the Hexapedal Hosts, Hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)benzene and 1,2,3,5,6,7-Hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)naphthalene

The 2-hexanone inclusion compounds of hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)benzene and 1,2,3,5,6,7-hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)naphthalene have been prepared and characterised by single crystal X-ray diffraction and thermal analysis. The kinetic parameters and mechanisms for the desolvation reaction have also been determined for both compounds.     

Preparation and near-infrared optical limiting property of fluorene-containing functional polyacetylene

A novel functional polyacetylene containing fluorene group as a pendant,poly（2-（p-methylstyrene）-7-acetylene-9,9-dioctyl-fluorene）, was synthesized in moderate yield by[Rh（nbd）Cl]₂-Et₃N catalyst.The structures and properties of monomer and polymer were characterized and evaluated with FTIR,NMR,UV-vis,GPC and Z-scan,respectively.The results show that the incorporation of fluorene into polyacetylene has endowed the resultant polymer with well optical limiting properties for laser at wavelength 780 nm based on two-photon absorption mechanism.     

Synthesis and properties of an ionic polyacetylene with aromatic heterocycles

A new ionic polyacetylene with two aromatic heterocycles (pyridyl and thienyl) was prepared by the activation polymerization of 2‐ethynylpyridine by using 3‐(6‐bromohexyloxy)methylthiophene without any additional initiator or catalyst. The activated acetylenic triple bond of N‐substituted‐2‐ethynylpyridinium bromide, formed at first quaternarization process, was susceptible to linear polymerization. The instrumental analysis data on the polymer structure revealed that the polymer have the conjugated polyene backbone structure with the designed two aromatic heterocycles. The photoluminescence peak is located at 510 nm corresponding to a photon energy of 2.43eV. The electrochemical properties of this ionic polyacetylene were also measured and discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5679–5685, 2007     

Polymerization of Styrene by Neutral Ni (II) Acetylide Complex

Over the past few years, the utilization of late transition metal-based soluble complexes as styrene polymerization catalysts has received considerable attention1. Various systems have been explored. For example, cationic h3-allylnickel complexes alone2 or modified by P (III) ligands3 as well as a few other systems (e. g., cationic h3-benzylic nickel complexes4) are active homogeneous catalysts for the low molecular weight polymerization of styrene by simple cationic mechanism2,3,4. Neut…     

Synthesis and characterization of an ionic conjugated polymer: Poly[2‐ethynyl‐N‐(2‐thiophenecarbonyl) pyridinium chloride]

The activated polymerization of 2‐ethynylpyridine by using 2‐thiophenecarbonyl chloride yielded the corresponding conjugated ionic polymer, poly[2‐ethynyl‐N‐(2‐thiophenecarbonyl)pyridinium chloride] (PETCPC). The polymerization proceeded well to give high yield of polymer without any additional initiator or catalyst. The instrumental analysis data on polymer structure indicated that the present ionic polymer have a conjugated polymer backbone system having N‐(2‐thiophenecarbonyl)pyridinium chloride as substituents. The photoluminescence maximum peak of PETCPC was located at 573 nm, which corresponds to the photon energy of 2.16 eV. The aromatic functional substituents in the conjugated backbone system shift PL maximum values because it makes different molecule arrangement. The cyclovoltamograms of PETCPC exhibited the electrochemically stable window at ?1.24 to 1.80 V region. It was found that the kinetics of the redox process of polymer might be controlled by the reactant diffusion process from the experiment of the oxidation current density of polymer versus the scan rate. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6153–6162, 2009     

A neutral Ni(II) acetylide-mediated radical polymerization of methyl methacrylate using the atom transfer radical polymerization method

A neutral nickel σ-acetylide complex [Ni(CCPh)₂(PBu₃)₂] (NBP) is used for possible atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in conjunction with an organic halide as an initiator [R-X: CCl₄, CH₃Cl, BrCCl₃, C₂H₅Br, and C₅H₉Br] in toluene at 80 °C. Among these initiating systems, BrCCl₃/NBP gave the best controlled radical polymerization of MMA and produced polymer with relatively narrow molecular weight distribution (M_w/M_n≈1.3). The ATRP of MMA is preliminarily identified by the following facts: (1) the present MMA polymerization initiated by BrCCl₃/NBP is completely hindered by the addition of TEMPO; (2) the conversion shows a typical linear variation with time in semilogarithmic coordinates; (3) the measured number-average molecular weights of polymer show a linear increase with conversion and agree closely with the theoretical values; (4) the resulting polymer chain contains a dormant carbon-halogen terminal.     

老化对聚(1-三甲基硅基-1-丙炔)气体渗透性能的影响

采用溶液浇铸法,制备了厚度为50~202 μm的聚(1-三甲基硅基-1-丙炔)(PTMSP)膜,研究了膜厚度、储存温度以及储存气氛对其气体渗透性能的影响。 在室温下储存时,PTMSP膜发生物理老化,气体渗透系数先是迅速下降,然后缓慢降低并趋向平稳。 在空气气氛中的下降速率要略大于在N2气气氛中。 气体渗透系数的下降速率随膜厚度的减小而增大。 在高温(100 ℃)空气气氛中,受物理及化学老化的共同作用,PTMSP膜气体渗透系数的下降速率进一步增大,IR谱图表明,聚合物氧化生成了C=O等极性基团。 随储存时间的延长,溶解度系数基本不变,扩散系数的下降是导致气体渗透系数下降的主要原因,这与聚合物体积松弛和(或)致密化及极性基团的形成所造成的自由体积的减小紧密相关。     

Polymerization of 1-chloro-2-β-naphthylacetylene by Mo catalysts and polymer properties

1-Chloro-2-β-naphthylacetylene (ClβNA) polymerized in good yields in the presence of MoCl₅-based catalysts. The highest weight-average molecular weight of poly(ClβNA) reached about 3 × 10⁵. The polymer was a yellow solid (absorption cutoff in CHCl₃ 450 nm). It was soluble in toluene, chloroform, etc., and provided a tough film by the solvent casting method. The polymer retained its weight up to 300°C in air; it was thermally less stable than poly(1-chloro-2-phenylacetylene) but more stable than poly(β-naphthylacetylene). The oxygen permeability coefficient (P_O2) of this polymer was 19 barrers (25°C), which is fairly small for a substituted polyacetylene. © 1996 John Wiley & Sons, Inc.     

New neutral Ni(II)- and Pd(II)-based initiators for polymerization of styrene

Neutral nickel and palladium σ-acetylide complexes [Ni(CCPh)₂(PBu₃)₂] and [Pd(CCPh)₂(PBu₃)₂] are novel initiators for the polymerization of styrene in CHCl₃ over a range of polymerization temperature from 40 to 60 °C. Between them, the nickel catalyst exhibited much higher activity than the palladium catalyst. The polystyrene obtained with Ni(II) initiator was a syndio-rich atactic polymer and its weight-average molecular weight reached 279 000. The mechanism of the polymerization was discussed and a radical mechanism was proposed.     

Alcoholysis of 2,2-Dichloropropyl Derivatives of Carbazole, Phenothiazine, and Phenoxazine

Reactions of 9-(2,2-dichlorocyclopropyl)carbazole, 10-(2,2-dichlorocyclopropyl)phenothiazine, and 10-(2,2-dichlorocyclopropyl)phenoxazine with alcohols in the system t-BuOK-DMSO yield the corresponding N-(1-alkoxy-2-propynyl) derivatives. Hydrolysis of 9-(1-methoxy-2-propynyl)carbazole and 10-(1-methoxy-2-propynyl)phenothiazine in 60% aqueous dioxane in the presence of sulfuric acid gives the corresponding heterocyclic amine and 2-propynal.     

A novel low‐bandgap conjugated polymer based on Ru(II) bis(acetylide) complex and BODIPY moieties

A novel conjugated polymer P‐1 incorporating Ru(II) bis(acetylide) complex and borondipyrromethene (BODIPY) moieties in the main chain was synthesized by Pd‐catalyzed Sonogashira coupling reaction of diethynyl substituted BODIPY derivative ( M‐1 ) and Ru(II) bis(acetylide) complex ( M‐2 ), and the reference polymer P‐2 was obtained from the same method as preparation of P‐1 . Compared with P‐2 , Ru(II)‐containing polymer P‐1 shows low‐bandgap as 0.87 eV from cyclic voltammetry, and obvious redshifts in both UV–vis absorption and fluorescence spectra. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1686–1692     

A practical synthesis of 5-(chloromethyl)furo[2,3-b]pyridine,a key intermediate for the HIV protease inhibitor,L-754,394

A practical synthesis of 5-(chloromethyl)furo[2,3-b]pyridine ( 10 ), the side chain used to incorporate a key pharmacophore of the HIV protease inhibitor, L-754,394, is described. The synthesis was accomplished in ten steps and in 15% overall yield from commercially available methyl 2-furoate.     

(±)-金锦香酸二甲酯甲醚的合成

本文以呋喃甲酸甲酯为原料, 经羟烷基化反应, 醇解反应和O-甲基化反应合成(±)-金锦香酸二甲酯甲醚。同时, 还发现了制备2-乙烯基呋喃衍生物的新方法。     

Synthesis of Polynuclear Nonfused Azoles

Polynuclear blocks consisting of nonfused heterocycles of the azole series, connected through methylene bridges, were synthesized by successive addition of azole units via cycloaddition of organic azides to the triple bond of N-(2-propynyl)azoles, as well as via reaction of azide ion at the cyano group of cyanomethylazoles. Initial N-(2-propynyl)azoles were prepared by reaction of 2-propynyl bromide with 1,2,3-triazoles, benzotriazole, and tetrazoles; cyanomethylazoles were obtained by alkylation of azoles with chloroacetonitrile. An analogous scheme was used to add heterocyclic units to 2-phenyl-1,2,3-triazole-4-carbonitrile. In this case, the first two heterocyclic units are linked through the ring carbon atom.     

Regioselective palladium-catalyzed arylation of 3-carboalkoxy furan and thiophene

[reaction: see text] The regioselective palladium(0)-catalyzed arylation of 3-furoate and 3-thiophenecarboxylate esters with aryl bromides is described. Conditions were developed that allow for the selective synthesis of either 2-aryl or 5-aryl products.     

Acetylenchemie 12. Mitt.: Weitere studien über die phasentransfer-katalysierte umsetzung des 9(10H)-acridinons mil alkinylhalogeniden

By the phase transfer catalyzed reaction of 9(10H)-acridinone with 1-bromo-2-propyne, 10-(2-propynyl)-9(10H)-acridinone is synthesized. As prototropic rearrangement products of this 10-(1,2-propadienyl)-9(10H)-acridinone and 10-(1-propynyl)-9(10H)-acridinone are obtained, Under the given conditins 1-bromo-2butyne leads to 10-(2-butynyl)-9(10H)-acridinone and 2-chloro-3-butyne leads to 10-(1-methyl-1,2-propddienyl)-9(10H)-acridinone, 10-(1-methyl-2-propynyl)-9(10H)-acridinone, 9-(1-methyl-2-propynyloxy)acridine and 10-[1-methyl-3-(3,4-dimethylphenyl-2-propynyl)]-9(10H)-acridinone. The formation of the products is experimentally confirmed and with published work compared.     

Novel Synthesis of 1-(1,2,3,5,6,7-Hexahydro- s-indacen-4-yl)-3-[4-(1-hydroxy-1-methyl-ethyl)-furan-2-sulfonyl]urea,an Anti-inflammatory Agent

Abstract

A novel synthesis of the anti-inflammatory agent 1-(1,2,3,5,6,7- hexahydro-s-indacen-4-yl)-3-[4-(1-hydroxy-1-methyl-ethyl)-furan-2-sulfonyl] urea 1 is described. Sulfonamide 5 was prepared starting from ethyl 3-furoate 2. Key steps were a one-pot sulfonylation with chlorosulfonic acid in methylene chloride followed by pyridinium salt formation and reaction with phosphorus pentachloride to provide ethyl 2-(chlorosulfonyl)-4-furoate 7. This sulfonyl chloride was treated with ammonium bicarbonate to form sulfonamide 8, followed by treatment with excess methyl magnesium chloride to provide 4-(1-hydroxy-1-methyl-ethyl)-furan-2-sulfonamide 5. 4-Isocyanato-1,2,3,5,6,7-hexahydro-s-indacene 16 was prepared from indan in five steps. The formation of the desired sulfonyl urea was carried out both with the isolated isocyanate 16 and via an in situ method.