cas 2628-17-3, 4-Hydroxystyrene | Articles data

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Synthesis method of hydroxyl-substituted styrene compound and synthesis method of photoresist resin monomer
The present invention provides a synthesis method of a hydroxyl-substituted styrene compound and a synthesis method of photoresist resin monomer. The synthesis method of the hydroxyl-substituted styrene compound comprises the following steps: a) the compound of formula I-1 is reacted with the Wetting reagent to obtain a compound of formula I-2. The synthesis method of the photoresist resin monomer comprises the following steps: a) the synthesis method of the styrene compound substituted with the above hydroxyl group to obtain a compound of formula I-2; b) the compound of formula I-2 is reacted with an acylating reagent to obtain the photoresist resin monomer, the structural formula is referred to formula I-3. The synthesis method of hydroxyl-substituted styrene compounds and photoresist resin monomers of the present invention has high yield and high purity.
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Paragraph 0006; 0083-0085

(2022/01/12)

MODIFIED MONOMER, MODIFIED POLYMER COMPRISING THE SAME AND METHOD FOR PREPARING THEM
A modified monomer useful for the polymer modification of formula 1. The present invention relates to a method for preparing a modified monomer, a modified polymer comprising a modified monomer-derived functional group, a rubber composition comprising the modified polymer, and a molded article produced from the rubber composition.
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Paragraph 0188-0191

(2021/05/18)

Copper(ii)-catalyzed protoboration of allenes in aqueous media and open air
A method has been developed for the facile Cu(ii)-catalyzed protoboration of monosubstituted allenes in aqueous media under atmospheric conditions. The reaction occurs site selectively, favoring internal alkene protoboration to afford 1,1-disubstituted vinylboronic acid derivatives (up to 93?:?7) with modest to good yields. The method has been applied to a variety of phenylallene derivatives as well as alkyl-substituted allenes. This journal is
Nekvinda, Jan,Santos, Webster L.,Snead, Russell F.
supporting information
p. 14925 - 14931
(2021/09/04)

Site-Selective Acceptorless Dehydrogenation of Aliphatics Enabled by Organophotoredox/Cobalt Dual Catalysis
The value of catalytic dehydrogenation of aliphatics (CDA) in organic synthesis has remained largely underexplored. Known homogeneous CDA systems often require the use of sacrificial hydrogen acceptors (or oxidants), precious metal catalysts, and harsh reaction conditions, thus limiting most existing methods to dehydrogenation of non- or low-functionalized alkanes. Here we describe a visible-light-driven, dual-catalyst system consisting of inexpensive organophotoredox and base-metal catalysts for room-temperature, acceptorless-CDA (Al-CDA). Initiated by photoexited 2-chloroanthraquinone, the process involves H atom transfer (HAT) of aliphatics to form alkyl radicals, which then react with cobaloxime to produce olefins and H2. This operationally simple method enables direct dehydrogenation of readily available chemical feedstocks to diversely functionalized olefins. For example, we demonstrate, for the first time, the oxidant-free desaturation of thioethers and amides to alkenyl sulfides and enamides, respectively. Moreover, the system's exceptional site selectivity and functional group tolerance are illustrated by late-stage dehydrogenation and synthesis of 14 biologically relevant molecules and pharmaceutical ingredients. Mechanistic studies have revealed a dual HAT process and provided insights into the origin of reactivity and site selectivity.
Zhou, Min-Jie,Zhang, Lei,Liu, Guixia,Xu, Chen,Huang, Zheng
supporting information
p. 16470 - 16485
(2021/10/20)

Discovery, Biocatalytic Exploration and Structural Analysis of a 4-Ethylphenol Oxidase from Gulosibacter chungangensis
The vanillyl-alcohol oxidase (VAO) family is a rich source of biocatalysts for the oxidative bioconversion of phenolic compounds. Through genome mining and sequence comparisons, we found that several family members lack a generally conserved catalytic aspartate. This finding led us to study a VAO-homolog featuring a glutamate residue in place of the common aspartate. This 4-ethylphenol oxidase from Gulosibacter chungangensis (Gc4EO) shares 42 % sequence identity with VAO from Penicillium simplicissimum, contains the same 8α-N3-histidyl-bound FAD and uses oxygen as electron acceptor. However, Gc4EO features a distinct substrate scope and product specificity as it is primarily effective in the dehydrogenation of para-substituted phenols with little generation of hydroxylated products. The three-dimensional structure shows that the characteristic glutamate side chain creates a closely packed environment that may limit water accessibility and thereby protect from hydroxylation. With its high thermal stability, well defined structural properties and high expression yields, Gc4EO may become a catalyst of choice for the specific dehydrogenation of phenolic compounds bearing small substituents.
Alvigini, Laura,Fraaije, Marco W.,Gran-Scheuch, Alejandro,Guo, Yiming,Mattevi, Andrea,Saifuddin, Mohammad,Trajkovic, Milos
p. 3225 - 3233
(2021/10/04)

Rapid synthesis method of biomass-based olefin
The invention discloses a rapid synthesis method of biomass-based olefin, which comprises the following steps: by taking a biomass ketone compound as a substrate and 2-pentanol as a hydrogen source and a solvent at the same time, under the action of hafnium/zirconium-based catalysts such as hafnium phenylphosphonate and Zirconium phenylphosphonate, hafnium phytate andzirconium phytate and hafnium polydivinylphenylphosphonate and zirconium polydivinylphenylphosphonate, selectively converting a biomass-based ketone compound into a corresponding alcohol compound, and continuously dehydrating to prepare olefin. According to the present invention, the time required by the system reaction is substantially shortened and is at least 2 h, the target product selectivity is significantly improved, the conversion rate of the representative reaction 4 '-methoxypropiophenone can at least achieve 99.8%, and the anethole yield can achieve 98.1%.
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Paragraph 0020; 0041-0048

(2021/07/31)

Two-photon induced isomerization through a cyaninic molecular antenna in azo compounds
We present a new design for non-linear optically responsive molecules based on a modular scheme where a polymethinic antenna section with important two-photon absorption properties is bonded to an isomerizable actuator section composed of a stilbenyl-azopyrrole unit. Upon two photon excitation, energy migration from the antenna-localized second singlet excited state to the stilbenyl-azopyrrole section allows for efficient indirect excitation and phototransformation of this actuator.
Villatoro, Emmanuel,Mu?oz-Rugeles, Leonardo,Durán-Hernández, Jesús,Salcido-Santacruz, Bernardo,Esturau-Escofet, Nuria,López-Cortés, Jose G.,Ortega-Alfaro, M. Carmen,Peón, Jorge
supporting information
p. 3123 - 3126
(2021/04/02)

Cross-Coupling Reactions with 2-Amino-/Acetylamino-Substituted 3-Iodo-1,4-naphthoquinones: Convenient Synthesis of Novel Alkenyl- And Alkynylnaphthoquinones and Derivatives
Functionalized 1,4-naphthoquinones have been employed as versatile synthons in organic synthesis, in addition to presenting a large array of biological activities. Herein, the applications of 2-amino-/ acetylamino-substituted 3-iodo-1,4-naphthoquinones in cross-coupling reactions are described to successfully afford sixteen novel 3-styryl-1,4-naphthoquinones (amino-stilbene-quinone hybrids) and four 3-alkynyl-1,4-naphthoquinone in overall good yields. Interestingly, the alkynylated derivatives could be obtained from ligand- and Pd-free Cu I -mediated cross-coupling reactions, after extensive investigations to exclude Pd as a co-catalyst. Lastly, the desilanized terminal alkyne was subjected to click chemistry reactions to give two novel triazole-1,4-naphthoquinone hybrids.
Demidoff, Felipe C.,Rodrigues Filho, Eduardo José P.,De Souza, Andréa Luzia F.,Netto, Chaquip D.,De Carvalho, Leandro L.
supporting information
p. 4097 - 4109
(2021/08/31)

Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis
N-Heterocyclic carbene (NHC) catalysis has emerged as a versatile tool in modern synthetic chemistry. Further increasing the complexity, several processes have been introduced that proceed via dual catalysis, where the NHC organocatalyst operates in concert with a second catalytic moiety, significantly enlarging the reaction scope. In biological transformations, multiple catalysis is generally used to access complex natural products. Guided by that strategy, triple catalysis has been studied recently, where three different catalytic modes are merged in a single process. In this Communication, direct α-C-H acylation of various alkenes with aroyl fluorides using NHC, sulfinate, and photoredox cooperative triple catalysis is reported. The method allows the preparation of α-substituted vinyl ketones in moderate to high yields with excellent functional group tolerance. Mechanistic studies reveal that these cascades proceed through a sequential radical addition/coupling/elimination process. In contrast to known triple catalysis processes that operate via two sets of interwoven catalysis cycles, in the introduced process, all three cycles are interwoven.
Liu, Kun,Studer, Armido
supporting information
p. 4903 - 4909
(2021/05/04)

Rapid biosynthesis of phenolic glycosides and their derivatives from biomass-derived hydroxycinnamates
Biomass-derived hydroxycinnamates (mainly includingp-coumaric acid and ferulic acid), which are natural sources of aromatic compounds, are highly underutilized resources. There is a need to upgrade them to make them economically feasible. Value-added phenolic glycosides and their derivatives, both belonging to a class of plant aromatic natural products, are widely used in the nutraceutical, pharmaceutical, and cosmetic industries. However, their complex aromatic structures make their efficient biosynthesis a challenging process. To overcome this issue, we created three novel synthetic cascades for the biosynthesis of phenolic glycosides (gastrodin, arbutin, and salidroside) and their derivatives (hydroquinone, tyrosol, hydroxytyrosol, and homovanillyl alcohol) fromp-coumaric acid and ferulic acid. Moreover, because the biomass-derived hydroxycinnamates directly provided aromatic units, the cascades enabled efficient biosynthesis. We achieved substantially high production rates (up to or above 100-fold enhancement) relative to the glucose-based biosynthesis. Given the ubiquity of the aromatic structure in natural products, the use of biomass-derived aromatics should facilitate the rapid biosynthesis of numerous aromatic natural products.
Zhao, Mingtao,Hong, Xulin,Abdullah,Yao, Ruilian,Xiao, Yi
p. 838 - 847
(2021/02/09)

The Stereoselective Oxidation of para-Substituted Benzenes by a Cytochrome P450 Biocatalyst
The serine 244 to aspartate (S244D) variant of the cytochrome P450 enzyme CYP199A4 was used to expand its substrate range beyond benzoic acids. Substrates, in which the carboxylate group of the benzoic acid moiety is replaced were oxidised with high activity by the S244D mutant (product formation rates >60 nmol.(nmol-CYP)?1.min?1) and with total turnover numbers of up to 20,000. Ethyl α-hydroxylation was more rapid than methyl oxidation, styrene epoxidation and S-oxidation. The S244D mutant catalysed the ethyl hydroxylation, epoxidation and sulfoxidation reactions with an excess of one stereoisomer (in some instances up to >98 %). The crystal structure of 4-methoxybenzoic acid-bound CYP199A4 S244D showed that the active site architecture and the substrate orientation were similar to that of the WT enzyme. Overall, this work demonstrates that CYP199A4 can catalyse the stereoselective hydroxylation, epoxidation or sulfoxidation of substituted benzene substrates under mild conditions resulting in more sustainable transformations using this heme monooxygenase enzyme.
Chao, Rebecca R.,Lau, Ian C.-K.,Coleman, Tom,Churchman, Luke R.,Child, Stella A.,Lee, Joel H. Z.,Bruning, John B.,De Voss, James J.,Bell, Stephen G.
supporting information
p. 14765 - 14777
(2021/09/14)

Amino Group Functionalized Hf-Based Metal-Organic Framework for Knoevenagel-Doebner Condensation
A Hf(IV) metal-organic framework (MOF) with di-amino functionalized linker was obtained as a crystalline solid with UiO-67 topology under solvothermal reaction conditions. The guest free form of Hf(IV) MOF (1′) was efficiently employed as a heterogeneous catalyst to synthesize cinnamic acid derivatives via Knoevenagel-Doebner reaction for the first time. The catalyst (1′) was efficiently active to directly achieve cinnamic acid from benzaldehyde and malonic acid. The solid retained its activity up to 6th cycle with no decay in its activity. The noticeable advantages of the catalyst are its milder reaction conditions, high yield, high stability, recyclable nature towards catalysis and wide substrate scope as well as shape-selective behaviour. The possible mechanism of the reaction was also studied thoroughly with suitable control experiments.
Das, Aniruddha,Anbu, Nagaraj,Gogoi, Chiranjib,Dhakshinamoorthy, Amarajothi,Biswas, Shyam
p. 3396 - 3403
(2021/08/20)

Supramolecular gels derived from nucleoside based bolaamphiphiles as a light-sensitive soft material
Light-sensitive Low Molecular Weight Gelators (LMWGs) derived from glyconucleoside bolaamphiphiles containing a stilbene unit displayed gelation abilities in hydroalcoholic mixtures. These materials showed a gel-sol transition under UV irradiation thanks to E-Z isomerization of stilbene and could find potential applications as drug delivery systems.
Baillet, Julie,Gaubert, Alexandra,Bassani, Dario M.,Verget, Julien,Latxague, Laurent,Barthélémy, Philippe
supporting information
p. 3397 - 3400
(2020/03/30)

Monitoring hydroxycinnamic acid decarboxylation by lactic acid bacteria using high-throughput UV-Vis spectroscopy
Hydroxycinnamic acid (HCA) decarboxylation by lactic acid bacteria (LAB) results in the production of 4-vinylplenols with great impact on the sensorial characteristics of foods. The determination of LAB decarboxylating capabilities is key for optimal strain selection for food production. The activity of LAB strains from the Ohio State University-Parker Endowed Chair (OSU-PECh) collection potentially capable of synthesizing phenolic acid decarboxylase was evaluated after incubation with HCAs for 36 h at 32 °C. A high-throughput method for monitoring HCAs decarboxylation was developed based on hypsochromic shifts at pH 1.0. Out of 22 strains evaluated, only Enterococcus mundtii, Lactobacillus plantarum and Pediococcus pentosaceus were capable of decarboxylating all p-coumaric, caffeic and ferulic acids. Other strains only decarboxylated p-coumaric and caffeic acid (6), only p-coumaric acid (2) or only caffeic acid (1), while 10 strains did not decarboxylate any HCA. p-Coumaric acid had the highest conversion efficiency, followed by caffeic acid and lastly ferulic acid. Results were confirmed by HPLC-DAD-ESI-MS analyses, showing the conversion of HCAs into their 4-vinylphenol derivatives. This work can help improve the sensory characteristics of HCA-rich foods where fermentation with LAB was used during processing.
García-Cano, Israel,Giusti, M. Monica,Jiménez-Flores, Rafael,Miyagusuku-Cruzado, Gonzalo,Rocha-Mendoza, Diana
(2020/08/24)

Phosphorus- And Sulfur-Containing High-Refractive-Index Polymers with High Tg and Transparency Derived from a Bio-Based Aldehyde
Two flexible and colorless polymers are synthesized based on a phosphorus-containing derivative of a bio-based aromatic aldehyde (4-hydroxybenzaldehyde) by a thiol-ene reaction. Thanks to the high polarizability of phosphorus and sulfur atoms, two polymers display refractive index (n) values of 1.721 and 1.698 at 546 nm, respectively. These data are much higher than those of polyphosphonates (below 1.65) and are comparable to those of polyphosphazenes with undesirable halogens (1.664-1.755). Moreover, both the polymers (TVP-TH1 and TVP-TH2) exhibit a transmittance of above 88% in the wavelength range from 550 to 2000 nm and a transmittance of about 0% in the UV region, indicating their potential application as transparent coatings for hindering the ultraviolet ray and infrared transmitting materials. In particular, these phosphorous-sulfide polymers display good thermostability with a glass transition temperature (Tg) of above 130 °C and 5% weight loss temperature (T5d) of over 310 °C. These results imply that new phosphorous-sulfide polymers are very suitable as encapsulation resins for light-emitting diodes (LEDs) and optical materials and as antireflective coatings and microlenses for the image sensors of complementary metal oxide semiconductors (CMOSs).
Fang, Linxuan,Sun, Jing,Chen, Xiaoyao,Tao, Yangqing,Zhou, Junfeng,Wang, Caiyun,Fang, Qiang
p. 125 - 131
(2020/02/04)

Metal-free and base-free decarboxylation of substituted cinnamic acids in a deep eutectic solvent
A metal-free and base-free strategy was developed in DES to synthesize styrenes for the first time by decarboxylation of cinnamic acid derivatives, which provided a renewable and cost efficiently protocol to access various styrenes including those with functional groups such as 4-vinylphenol and 1-chloro-4-vinylbenzene.
Chen, Chen,Jian, Yuqing,Lei, Yuxin,Li, Bin,Peng, Caiyun,Sheng, Wen-Bing,Sumera, Yasmin,Wang, Wei,Zhang, Ming
p. 558 - 563
(2020/01/24)

Palladium-Catalyzed Hydroxylation of Aryl Halides with Boric Acid
Boric acid, B(OH)3, is proved to be an efficient hydroxide reagent in converting (hetero)aryl halides to the corresponding phenols with a Pd catalyst under mild conditions. Various phenol products were obtained in good to excellent yields. This transformation tolerates a broad range of functional groups and molecules, including base-sensitive substituents and complicated pharmaceutical (hetero)aryl halide molecules.
Song, Zhi-Qiang,Wang, Dong-Hui
supporting information
p. 8470 - 8474
(2020/11/18)

Selective hydrodeoxygenation of hydroxyacetophenones to ethyl-substituted phenol derivatives using a FeRu?SILP catalyst
The selective hydrodeoxygenation of hydroxyacetophenone derivatives is achieved opening a versatile pathway for the production of valuable substituted ethylphenols from readily available substrates. Bimetallic iron ruthenium nanoparticles immobilized on an imidazolium-based supported ionic liquid phase (Fe25Ru75?SILP) show high activity and stability for a broad range of substrates without acidic co-catalysts. This journal is
Bordet, Alexis,Goclik, Lisa,Leitner, Walter,Offner-Marko, Lisa
supporting information
p. 9509 - 9512
(2020/09/02)

Synthesis and evaluation of resveratrol derivatives as fetal hemoglobin inducers
Resveratrol (RVT) derivatives (10a-i) were designed, synthesized, and evaluated for their potential as gamma-globin inducers in treating Sickle Cell Disease (SCD) symptoms. All compounds were able to release NO at different levels ranging from 0 to 26.3percent, while RVT did not demonstrate this effect. In vivo, the antinociceptive effect was characterized using an acetic acid-induced abdominal contortion model. All compounds exhibited different levels of protection, ranging from 5.9 to 37.3percent; the compound 10a was the most potent among the series. At concentrations between 3.13 and 12.5 μM, the derivative 10a resulted in a reduction of 41.1–64.3percent in the TNF-α levels in the supernatants of macrophages that were previously LPS-stimulated. This inhibitory effect was higher than that of RVT used as the control. In addition, the compound 10a and RVT induced double the production of the gamma-globin chains (γG + γA), compared to the vehicle, using CD34+ cells. Compound 10a also did not induce membrane perturbation and it was not mutagenic in the in vivo assay. Thus, compound 10a emerged as a new prototype of the gamma-globin-inducer group with additional analgesic and anti-inflammatory activities and proving to be a useful alternative to treat SCD symptoms.
Andersen, Olaf Sparre,Barbieri, Karina Pereira,Bosquesi, Priscila Longhin,Carlos, Iracilda Zepone,Chelucci, Rafael Consolin,Costa, Fernando Ferreira,Dos Santos, Jean Leandro,Fernandes, Guilherme Felipe dos Santos,Lanaro, Carolina,Melchior, Aylime Castanho Bolognesi,Pavan, Aline Renata,Rusinova, Radda,de Souza, Cristiane Maria
(2020/05/25)

Method for preparing alcohol and phenol through aerobic hydroxylation reaction of boric acid derivative in absence of photocatalyst
The invention discloses a method for preparing alcohol and phenol through aerobic hydroxylation reaction of a boric acid derivative in the absence of a photocatalyst, wherein the boric acid derivativeis aryl boronic acid or alkyl boronic acid, and the corresponding target compounds are respectively a phenol-based compound and an alcohol-based compound. According to the method, by using a boric acid derivative as a reaction substrate, an additive is added under a solvent condition, and a hydroxylation reaction is performed under aerobic and illumination conditions to obtain a corresponding target compound. According to the invention, the new strategy is provided for the synthesis of phenols through aerobic hydroxylation of aryl boronic acid without a photocatalyst; the catalyst-free aerobic hydroxylation method for photocatalysis of aryl boronic acid or alkyl boronic acid by using triethylamine as an additive is firstly disclosed; and the new method has advantages of photocatalyst-freecondition, wide substrate range and good functional group compatibility.
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Paragraph 0025-0028; 0030-0032

(2020/01/25)

A Strategy To Obtain o-Naphthoquinone Methides: Ag(I)-Catalyzed Cyclization of Enynones for the Synthesis of Benzo[ h]chromanes and Naphthopyryliums
A new strategy to obtain o-NQM intermediates through a ring-formation strategy by Ag(I)-catalyzed cyclization of 2-alkenylphenyl alkynyl ketones and its [4 + 2] annulations with styrenes has been developed. This reaction features high efficiency, mild reaction conditions, as well as flexible substitutions and atom economy. The obtained benzo[h]chromane products were further oxidized to naphthopyryliums, which displayed tunable photophysical properties.
Wu, Feng,Zhu, Shifa
supporting information

(2019/03/08)

Aromatic vs. aliphatic hyperbranched polyphosphoesters as flame retardants in epoxy resins
The current trend for future flame retardants (FRs) goes to novel efficient halogen-free materials, due to the ban of several halogenated FRs. Among the most promising alternatives are phosphorus-based FRs, and of those, polymeric materials with complex shape have been recently reported. Herein, we present novel halogen-free aromatic and aliphatic hyperbranched polyphosphoesters (hbPPEs), which were synthesized by olefin metathesis polymerization and investigated them as a FR in epoxy resins. We compare their efficiency (aliphatic vs. aromatic) and further assess the differences between the monomeric compounds and the hbPPEs. The decomposition and vaporizing behavior of a compound is an important factor in its flame-retardant behavior, but also the interaction with the pyrolyzing matrix has a significant influence on the performance. Therefore, the challenge in designing a FR is to optimize the chemical structure and its decomposition pathway to the matrix, with regards to time and temperature. This behavior becomes obvious in this study, and explains the superior gas phase activity of the aliphatic FRs.
Markwart, Jens C.,Battig, Alexander,Velencoso, Maria M.,Pollok, Dennis,Schartel, Bernhard,Wurm, Frederik R.
(2019/11/11)

Poly[(side-on mesogen)-Alt-(end-on mesogen)]: A compromised molecular arrangement
In recent years, sequence-controlled side-chain liquid crystal polymers (SCLCPs) have gained extensive interest because mesogenic units with different lengths and distributions can form various ordered sequences, which further endow LCP materials with diverse functions. In this manuscript, a side-chain side-on maleimide-containing monomer 2,5-bis-(4-butoxy-benzoyloxy)-benzoic acid 6-(2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-hexyl ester (Y1801) and a side-chain end-on styrene-containing monomer 4′-[6-(4-vinyl-phenoxy)-hexyloxy]-biphenyl-4-carbonitrile (Y1802) are combined in one single macromolecular chain and orderly polymerized in an alternative sequence to form an alternating copolymer Poly(Y1801-Alt-Y1802). The chemical structure and alternating sequence of Poly(Y1801-Alt-Y1802) are confirmed by GPC and NMR techniques. The combination of DSC, POM, and WAXS data indicates that, although the side-on homopolymer PY1801 and the end-on homopolymer PY1802 both exhibit the nematic phase, their alternating copolymer Poly(Y1801-Alt-Y1802) shows an interdigitated smectic A phase, a compromised molecular arrangement instead. In addition, a strong fluorescence emission of Poly(Y1801-Alt-Y1802) is observed, which might provide this novel alternating-structured liquid crystal polymer with potential applications in luminescent materials and devices.
Wang, Meng,Bao, Wei-Wei,Chang, Wen-Ying,Chen, Xu-Man,Lin, Bao-Ping,Yang, Hong,Chen, Er-Qiang
p. 5791 - 5800
(2019/08/26)

Method for preparing p-hydroxystyrene from p-hydroxyacetophenone by hydrogenation reaction and coupling dehydration reaction in one step
The invention provides a method for preparing p-hydroxystyrene from p-hydroxyacetophenone by hydrogenation reaction and coupling dehydration reaction in one step. In the method, p-hydroxyacetophenoneis used as a reaction substrate, an alcohol is used as a solvent, and a one-step reaction is carried out under an alkaline condition, so that p-hydroxystyrene is produced. Compared with the prior art,the invention has the following advantages: (1) the preparation method adopts common p-hydroxyacetophenone as the substrate, and the hydrogenation reaction and the coupling dehydration reaction are carried out in one step for obtaining p-hydroxystyrene, the conversion rate of p-hydroxyacetophenone is 99% or more, the yield of a crude product of p-hydroxystyrene is 85%, and the yield of a pure product of p-hydroxystyrene is 76%; and (2) the method simplifies the production process, reduces the production cost, and has good economic value.
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Paragraph 0022; 0023; 0024; 0025; 0026-0031

(2019/04/18)

Method for preparing styrene derivative from ionic liquid
The invention belongs to the technical field of chemical engineering and pharmaceutical intermediate synthesis and relates to a method for preparing a styrene derivative from ionic liquid. The methodhas advantages that by adoption of the ionic liquid as a solvent, high reaction catalyzing efficiency is achieved; due to reusability of the ionic liquid, industrial production cost is saved, and theenvironment problem caused by traditional solvents can be solved helpfully.
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Paragraph 0023-0025; 0041-0046

(2019/04/06)

3D-Printed Phenacrylate Decarboxylase Flow Reactors for the Chemoenzymatic Synthesis of 4-Hydroxystilbene
Continuous flow systems for chemical synthesis are becoming a major focus in organic chemistry and there is a growing interest in the integration of biocatalysts due to their high regio- and stereoselectivity. Methods established for 3D bioprinting enable the fast and simple production of agarose-based modules for biocatalytic reactors if thermally stable enzymes are available. We report here on the characterization of four different cofactor-free phenacrylate decarboxylase enzymes suitable for the production of 4-vinylphenol and test their applicability for the encapsulation and direct 3D printing of disk-shaped agarose-based modules that can be used for compartmentalized flow microreactors. Using the most active and stable phenacrylate decarboxylase from Enterobacter spec. in a setup with four parallel reactors and a subsequent palladium(II) acetate-catalysed Heck reaction, 4-hydroxystilbene was synthesized from p-coumaric acid with a total yield of 14.7 % on a milligram scale. We believe that, due to the convenient direct immobilization of any thermostable enzyme and straightforward tuning of the reaction sequence by stacking of modules with different catalytic activities, this simple process will facilitate the establishment and use of cascade reactions and will therefore be of great advantage for many research approaches.
Peng, Martin,Mittmann, Esther,Wenger, Lukas,Hubbuch, Jürgen,Engqvist, Martin K. M.,Niemeyer, Christof M.,Rabe, Kersten S.
supporting information
p. 15998 - 16001
(2019/11/22)

Substituted styrene preparation method
The invention belongs to the technical field of synthesis of chemical and medical intermediates, and relates to a substituted styrene preparation method, in particular to a method for preparing substituted styrene by using an ionic solution. In the method, the ionic solution is used as a solvent, and the reaction catalyzing efficiency is high. The ionic solution can be repeatedly used, industrialproduction cost is saved, and environment problems caused by a traditional solvent are solved favorably.
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Paragraph 0023-0025; 0041-0045

(2019/02/26)

A method for the preparation of substituted styrene ion solution method
The invention belongs to chemical and pharmaceutical intermediate synthesis technology field, relates to a process for preparing a substituted styrene ion solution method. The method takes the ionic liquid as solvent, reaction of high catalytic efficiency. The ionic liquid can be used repeatedly, save the industrialized production cost, and to facilitate the solution of the environmental problem of traditional solvent.
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Paragraph 0023; 0024; 0025; 0041; 0042; 0043; 0044-0046

(2019/04/02)

Phenolic Bis-styrylbenzo[ c]-1,2,5-thiadiazoles as Probes for Fluorescence Microscopy Mapping of Aβ Plaque Heterogeneity
A fluorescent bis-styryl-benzothiadiazole (BTD) with carboxylic acid functional groups (X-34/Congo red analogue) showed lower binding affinity toward Aβ1-42 and Aβ1-40 fibrils than its neutral analogue. Hence, variable patterns of neutral OH-substituted bis-styryl-BTDs were generated. All bis-styryl-BTDs showed higher binding affinity to Aβ1-42 fibrils than to Aβ1-40 fibrils. The para-OH on the phenyl rings was beneficial for binding affinity while a meta-OH decreased the affinity. Differential staining of transgenic mouse Aβ amyloid plaque cores compared to peripheral coronas using neutral compared to anionic bis-styryl ligands indicate differential recognition of amyloid polymorphs. Hyperspectral imaging of transgenic mouse Aβ plaque stained with uncharged para-hydroxyl substituted bis-styryl-BTD implicated differences in binding site polarity of polymorphic amyloid plaque. Most properties of the corresponding bis-styryl-BTD were retained with a rigid alkyne linker rendering a probe insensitive to cis-trans isomerization. These new BTD-based ligands are promising probes for spectral imaging of different Aβ fibril polymorphs.
Zhang, Jun,Konsmo, Audun,Sandberg, Alexander,Wu, Xiongyu,Nystr?m, Sofie,Obermüller, Ulrike,Wegenast-Braun, Bettina M.,Konradsson, Peter,Lindgren, Mikael,Hammarstr?m, Per
p. 2038 - 2048
(2019/02/26)

Bio-based vinylphenol family: Synthesis via decarboxylation of naturally occurring cinnamic acids and living radical polymerization for functionalized polystyrenes
A series of bio-based vinylphenols or hydroxystyrenes is prepared by simple decarboxylation of various naturally occurring cinnamic acids such as o-, m-, and p-coumaric; caffeic; ferulic; and sinapinic acids, which possess hydroxy groups and other substituents at different positions on the aromatic ring. After protection of the phenolic moieties with trialkylsilyl groups, reversible addition–fragmentation chain-transfer polymerization is accomplished with cumyl dithiobenzoate to afford various bio-based hydroxyl-protected polystyrenes with controlled molecular weights and narrow molecular weight distributions. Subsequent deprotection of the silyl groups under mild conditions results in a series of well-defined functionalized polystyrenes possessing different numbers (mono-, di-, tri-) of hydroxy groups at different positions (o, m, p). The obtained functionalized polystyrenes show unique thermal properties depending on the substituents, and those with phenol and catechol groups serve as reducing agents for silver ions.
Takeshima, Hisaaki,Satoh, Kotaro,Kamigaito, Masami
(2019/08/20)

Iodonitrene in Action: Direct Transformation of Amino Acids into Terminal Diazirines and 15N2-Diazirines and Their Application as Hyperpolarized Markers
A one-pot metal-free conversion of unprotected amino acids to terminal diazirines has been developed using phenyliodonium diacetate (PIDA) and ammonia. This PIDA-mediated transformation occurs via three consecutive reactions and involves an iodonitrene intermediate. This method is tolerant to most functional groups found on the lateral chain of amino acids, it is operationally simple, and it can be scaled up to provide multigram quantities of diazirine. Interestingly, we also demonstrated that this transformation could be applied to dipeptides without racemization. Furthermore, 14N2 and 15N2 isotopomers can be obtained, emphasizing a key trans-imination step when using 15NH3. In addition, we report the first experimental observation of 14N/15N isotopomers directly creating an asymmetric carbon. Finally, the 15N2-diazirine from l-tyrosine was hyperpolarized by a parahydrogen-based method (SABRE-SHEATH), demonstrating the products' utility as hyperpolarized molecular tag.
Colell, Johannes F. P.,Franck, Xavier,Glachet, Thomas,Marzag, Hamid,Reboul, Vincent,Saraiva Rosa, Nathalie,Theis, Thomas,Warren, Warren S.,Zhang, Guannan
(2019/09/06)

Pd-Catalyzed Synthesis of Vinyl Arenes from Aryl Halides and Acrylic Acid
Acrylic acid is presented as an inexpensive, non-volatile vinylating agent in a palladium-catalyzed decarboxylative vinylation of aryl halides. The reaction proceeds through a Heck reaction of acrylic acid, immediately followed by protodecarboxylation of the cinnamic acid intermediate. The use of the carboxylate group as a deciduous directing group ensures high selectivity for monoarylated products. The vinylation process is generally applicable to diversely substituted substrates. Its utility is shown by the synthesis of drug-like molecules and the gram-scale preparation of key intermediates in drug synthesis.
Gao, Yang,Ou, Yang,Goo?en, Lukas J.
supporting information
p. 8709 - 8712
(2019/06/17)

Photoinduced hydroxylation of arylboronic acids with molecular oxygen under photocatalyst-free conditions
Photoinduced hydroxylation of boronic acids with molecular oxygen under photocatalyst-free conditions is reported, providing a green entry to a variety of phenols and aliphatic alcohols in a highly concise fashion. This new protocol features photocatalyst-free conditions, wide substrate scope and excellent functional group compatibility.
Xu, Yu-Ting,Li, Chen-Yuan,Huang, Xiao-Bo,Gao, Wen-Xia,Zhou, Yun-Bing,Liu, Miao-Chang,Wu, Hua-Yue
supporting information
p. 4971 - 4975
(2019/09/30)

MODIFIED POLYMER, METHOD OF PREPARING THE SAME, AND RUBBER COMPOSITION INCLUDING THE MODIFIED POLYMER
The present invention relates to a modified polymer having a high modification ratio and an excellent affinity with a filler, a method of preparing the same, a rubber composition including the modified polymer, and a molded article prepared from the rubber composition. The modified polymer according to the present invention may exhibit a high modification ratio by including functional groups in a polymer main chain and on at least one end thereof, and thus, an affinity with a filler, such as silica, may be excellent. Also, the rubber composition according to the present invention may have excellent processability by including the modified polymer having an excellent affinity with the filler, and, as a result, a processed product (e.g., tire) prepared by using the rubber composition may have excellent tensile strength, abrasion resistance, and wet road surface resistance.
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Paragraph 0129; 0130; 0133; 0134

(2018/05/23)

Synthesis method of pterostilbene
The invention provides a synthesis method of pterostilbene. The synthesis method takes 4-hydroxybenzaldehyde as a raw material and comprises the following steps: carrying out acetylation reaction to generate 4-acetoxybenzaldehyde; then carrying out wittig reaction to generate 4-acetoxystyrene; carrying out hydrolysis reaction on 4-acetoxystyrene to generate 4-hydroxystyrene; carrying out Heck reaction on 4-hydroxystyrene to obtain a target product pterostilbene. The method provided by the invention has the advantages of easiness for obtaining the raw materials, high product selectivity, relatively high yield, moderate reaction conditions and simplicity in operation.
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Paragraph 0017; 0018; 0038; 0043

(2018/09/21)

Method for synthesizing hydroxystyrene compound by one-pot process
The invention relates to a method for synthesizing a hydroxystyrene compound by one-pot process. The method comprises the following steps of under the condition of normal pressure or decompression, enabling hydroxyl-substituted benzaldehyde, malonic acid or malonic acid derivative, an alkaline catalyst and a polymerization inhibitor to react for a first preset time in a first organic solvent at the first temperature suitable for the reflux of the first organic solvent, so as to obtain a first reaction mixture; heating the reaction system to a second temperature, and reacting for a second reaction time, so as to obtain a second reaction mixture; distilling the second reaction mixture to remove solvent, so as to obtain the hydroxystyrene compound. The method has the beneficial effects that the reaction temperature for the synthesizing of the hydroxystyrene compound is mild, and the yield rate of a final product is high.
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Paragraph 0056-0058; 0062-0064

(2018/10/24)

Terminal Alkenes from Acrylic Acid Derivatives via Non-Oxidative Enzymatic Decarboxylation by Ferulic Acid Decarboxylases
Fungal ferulic acid decarboxylases (FDCs) belong to the UbiD-family of enzymes and catalyse the reversible (de)carboxylation of cinnamic acid derivatives through the use of a prenylated flavin cofactor. The latter is synthesised by the flavin prenyltransferase UbiX. Herein, we demonstrate the applicability of FDC/UbiX expressing cells for both isolated enzyme and whole-cell biocatalysis. FDCs exhibit high activity with total turnover numbers (TTN) of up to 55000 and turnover frequency (TOF) of up to 370 min?1. Co-solvent compatibility studies revealed FDC's tolerance to some organic solvents up 20 % v/v. Using the in-vitro (de)carboxylase activity of holo-FDC as well as whole-cell biocatalysts, we performed a substrate profiling study of three FDCs, providing insights into structural determinants of activity. FDCs display broad substrate tolerance towards a wide range of acrylic acid derivatives bearing (hetero)cyclic or olefinic substituents at C3 affording conversions of up to >99 %. The synthetic utility of FDCs was demonstrated by a preparative-scale decarboxylation.
Aleku, Godwin A.,Prause, Christoph,Bradshaw-Allen, Ruth T.,Plasch, Katharina,Glueck, Silvia M.,Bailey, Samuel S.,Payne, Karl A. P.,Parker, David A.,Faber, Kurt,Leys, David
p. 3736 - 3745
(2018/08/03)

METHOD FOR THE SYNTHESIS AND PRODUCTION OF ALKENYL COMPOUND
PROBLEM TO BE SOLVED: To provide a method for producing an efficient alkenyl compound conveniently and inexpensively. SOLUTION: A first compound represented by formula (1) reacts with a second compound represented by formula (3), in the presence of amino acid, in solvent containing amine, in a range of 50-200°C, to produce an alkenyl compound represented by formula (A) [where R1 is hydrogen or an optionally substituted C1-C30 alkyl group, R2 is a carboxyl group or the like, R3 and R4 are hydrogen, an optionally substituted C1-C30 alkyl group or the like]. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0049; 0067; 0085

(2018/09/20)

Multienzyme One-Pot Cascade for the Stereoselective Hydroxyethyl Functionalization of Substituted Phenols
The operability and substrate scope of a redesigned vinylphenol hydratase as a single biocatalyst or as part of multienzyme cascades using either substituted coumaric acids or phenols as stable, cheap, and readily available substrates are reported.
Payer, Stefan E.,Pollak, Hannah,Schmidbauer, Benjamin,Hamm, Florian,Juri?i?, Filip,Faber, Kurt,Glueck, Silvia M.
supporting information
p. 5139 - 5143
(2018/09/13)

Electronically Mismatched Cycloaddition Reactions via First-Row Transition Metal, Iron(III)-Polypyridyl Complex
The iron(III)-polypyridyl complex and its derivatives showed sufficient oxidizing potential to act as a one-electron oxidant, producing radical cations from olefins and promoting the efficient radical cation [2 + 2] and [2 + 4] cycloaddition reactions. Subsequent chain propagation afforded trisubstituted cyclobutane or cyclohexene derivatives, and this facile route enables the replacement of rare metals with sustainable, green, and inexpensive iron in radical cation cycloadditions.
Shin, Jung Ha,Seong, Eun Young,Mun, Hyeon Jin,Jang, Yu Jeong,Kang, Eun Joo
supporting information
p. 5872 - 5876
(2018/09/25)

Multigram Scale Enzymatic Synthesis of (R)-1-(4′-Hydroxyphenyl)ethanol Using Vanillyl Alcohol Oxidase
The enantioselective oxyfunctionalisation of C?H bonds is a highly interesting reaction, as it provides access to chiral alcohols that are important pharmaceutical building blocks. However, it is hard to achieve using traditional methods. One way in which it can be achieved is through the action of oxidative enzymes. Although many reports of the oxyfunctionalisation capabilities of enzymes at an analytical scale have been published, reports on the use of enzymes to achieve oxyfunctionalisation on a synthetically relevant scale are fewer. Here, we describe the scale-up of the conversion of 4-ethylphenol to (R)-1-(4′-hydroxyphenyl)ethanol using the flavin-dependent enzyme vanillyl alcohol oxidase. The process was optimised by testing different reaction media and substrate and enzyme concentrations and by performing it under an oxygen atmosphere. Under optimised reaction conditions, 4.10 g (R)-1-(4′-hydroxyphenyl)ethanol at 97% ee was obtained from 10 g 4-ethylphenol (isolated yield 36%). These results highlight some of the challenges that can be encountered during scale-up of an enzymatic oxyfunctionalisation process to a synthetically relevant scale and will be of use for the development of enzymatic processes for the synthesis of industrially relevant compounds. (Figure presented.).
Ewing, Tom A.,Kühn, Jasmin,Segarra, Silvia,Tortajada, Marta,Zuhse, Ralf,van Berkel, Willem J. H.
supporting information
p. 2370 - 2376
(2018/06/20)

Recyclable CNT-chitosan nanohybrid film utilized in copper-catalyzed aerobic ipso-hydroxylation of arylboronic acids in aqueous media
A convenient heterogeneous catalytic system consisting of recyclable and reusable carbon nanotube-chitosan nanohybrid film and copper salt was developed for the aerobic ipso-hydroxylation of arylboronic acids. A variety of arylboronic acids bearing electron-withdrawing or electron-donating groups were smoothly transformed at room temperature in water to afford the corresponding phenols in high yields.
Kim, Han-Sem,Joo, Sung-Ryu,Shin, Ueon Sang,Kim, Seung-Hoi
p. 4597 - 4601
(2018/11/23)

Facile synthesis and characterization of highly branched polystyrene by self-condensing atom transfer radical polymerization
To simply prepare hyperbranched polystyrene with dendritic structure for optical and electronic applications, the copper-mediated self-condensing atom transfer radical polymerization of 4-(2-bromopropionyl)oxy styrene has been attempted. Given the unequal reactivity of two propagating species owing to different substituents which stabilize radicals, the influence of polymerization conditions on the structure of dendritic polystyrene were investigated. Higher polymerization temperature leaded to the lower functionality of Br in the branched polystyrene due to HBr elimination. As the catalyst to monomer ratio increased, the degree of branching of the prepared polystyrene was enhanced by increasing the reaction chance of the less stabilized propagating site.
Lee, Jun Hyup
p. 46 - 51
(2018/05/15)

4 - hydroxystyrene compound separation method (by machine translation)
[Problem] 4 - hydroxystyrene polymer does not contain volatile components produced by reaction a compound, 4 - hydroxystyrene separation method for obtaining high-purity of a compound. [Solution] 4 - hydroxystyrene compound, in the presence of a volatile solvent and a non-volatile solvent by distillation-thin, highly pure 4 - hydroxystyrene compound preparation can be obtained. The resulting formulation is stable with time, and can be applied to various applications and uses. [Drawing] no (by machine translation)
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Paragraph 0020

(2017/06/20)

Synthetic method of lipid-lowering drug ciprofibrate
The invention provides a synthetic method of lipid-lowering drug ciprofibrate. The synthetic method comprises the following steps: catalyzing reaction of p-hydroxy benzaldehyde and propane diacid in a mixed solvent by virtue of alkali, so as to generate p-hydroxystyrene; catalyzing reaction of p-hydroxystyrene, acetone, chloroform and alkali by virtue of a phase transfer catalyst, so as to generate an intermediate 2-methyl-2-(4-vinylphenoxy)propionic acid; and reacting 2-methyl-2-(4-vinylphenoxy)propionic acid with TiCl4, Mg and CCl4, so as to generate ciprofibrate. The synthetic method has the beneficial effects that the reaction route is short, the raw materials are cheap and easily available, reaction conditions are mild, the energy consumption is reduced, and the production cost is lowered; the post-processing step is simple, the emission of three wastes is reduced, and the method is environment-friendly and safe. Compared with routes of predecessors, the synthetic method has the advantages that the reaction selectivity and conversion rate of the route are relatively high, the wasting of the raw materials is reduced, and the economical efficiency is relatively high.
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Paragraph 0022; 0041; 0042; 0043; 0051; 0059; 0067; 0075

(2017/09/01)

Synthesis of Stilbene-Quinone Hybrids through Heck Reactions in PEG-400
Styrenes were coupled with 3-iodolawsone in PEG-400 at 90 °C, leading stereoselectively to (E)-stilbene-quinone hybrids through Heck reactions. The best reaction conditions were found to be the use of NaOH (3 equiv) and 10 mol% of palladium acetate at 90 °C for 15 minutes. The chemical yields of the Heck reactions using styrenes with electron-withdrawing groups (65-98%) were greater than styrenes bearing electron-donating groups (7-32%) on the aromatic ring. In particular, the chemical yields of Heck reactions involving nitrostyrenes were the best ones observed.
Demidoff, Felipe C.,De Souza, Fabrícia P.,Netto, Chaquip D.
supporting information
p. 5217 - 5223
(2017/11/28)

A method for preparing the fat cumaric acupoint of the c bethe method
The invention discloses a method for preparing a hypolipidemic medicine ciprofibrate with p-coumaric acid. The method comprises the following specific steps: p-coumaric acid (I) is subjected to a decarboxylation reaction under the effect of an alkaline catalyst, such that p-hydroxystyrene (II) is obtained; p-hydroxystyrene (II) is subjected to a reaction with 2-haloisobutyrate under the effect of alkali, such that an etherified product (III) is obtained; under an alkaline condition, the etherified product (III) and chloroform are subjected to a cyclization reaction under the effect of a phase transfer catalyst, such that a cyclized product (IV) is obtained; the cyclized product (IV) is subjected to alcoholysis and acidification in an alkali solution; and recrystallization is carried out, such that ciprofibrate (V) is obtained. The method provided by the invention has the advantages of short synthesis process, safe operation and easy post-treatment. The method is suitable for large-scale industrialized productions, and almost has no possibility of causing accidents such as explosion. During the entire reaction process, only conventional acid, alkali and solvent are used, such that the cost is low. The solvent can be recovered and reused, such that the method is environment-friendly. With the method, the yield is improved by more than 20%.
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Paragraph 0052; 0062; 0071-0072

(2017/10/07)

CSJ acting as a versatile highly efficient greener resource for organic transformations
Simple, new, greener and efficient alternatives to the existing protocols have been developed for the reduction of aromatic aldehydes to their corresponding alcohols, decarboxylation of substituted benzoic acids (C6-C1) and substituted cinnamic acids (C6-C3) with a hydroxyl group at the para position with respect to the acid group to corresponding phenolic compounds and vinyl phenols respectively by using a natural feedstock, cucumber juice (CSJ), which acts as a greener solvent system, performing a substrate-selective reaction. Additionally, the hydrolysis of the acetyl as well as the benzoyl group of aromatic compounds has been carried out to afford excellent yield by CSJ.
Maity, Himadri Sekhar,Misra, Kaushik,Mahata, Tanushree,Nag, Ahindra
p. 24446 - 24450
(2016/03/15)

Non-ionic photo-acid generating polymers for resist applications
Photo-acid generating vinyl polymerizable monomers (PAG monomers) were prepared comprising sulfonate ester groups of N-hydroxide imides. The photo-acid generating portion of the PAG monomer is linked to a polymerizable portion of the monomer by an amide linking group. Photo-acid generating polymers (PAG polymers) of the PAG monomers show high sensitivity to extreme ultraviolet radiation (13.5 nm) and much less sensitivity to far ultraviolet wavelengths (193 nm, 248 nm). The PAG polymers also exhibit thermal and chemical amplification properties useful for forming high resolution positive tone or negative tone lithographic resist patterns.
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(2016/02/15)

4-Vinylphenyl Glycidyl Ether: Synthesis, RAFT Polymerization, and Postpolymerization Modifications with Alcohols
4-Vinylphenyl glycidyl ether (4VPGE), an epoxide-containing styrenic monomer, was synthesized and then polymerized in a controlled fashion under reversible addition-fragmentation chain-transfer (RAFT) polymerization conditions using butyl 1-phenylethyl trithiocarbonate as the chain-transfer agent. The high degree of chain-end functionalization of the produced polymers was confirmed by chain extension reactions with styrene that afforded well-defined block copolymers. Phenyl glycidyl ether was utilized as a model compound to identify the optimal reaction conditions for alcoholysis of the glycidyl moiety using BF3 as a Lewis acid catalyst, and postpolymerization modifications were subsequently carried out on the epoxide groups of poly4VPGE with a library of structurally diverse alcohols to yield a number of β-hydroxy ether-functionalized polymers.
McLeod, David C.,Tsarevsky, Nicolay V.
p. 1135 - 1142
(2016/03/25)