- Carbon-13 chemical shift tensors in aromatic compounds. 3. Phenanthrene and triphenylene
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Measurements of the principal values of the 13C chemical shift tensor are presented for the three carbons in triphenylene and for three different α-carbons in phenanthrene. The measurements in triphenylene were made in natural abundance samples at room temperature, while the phenanthrene tensors were obtained from selectively labeled compounds (99% 13C) at low temperatures (～25 K). The principal values of the shift tensors were oriented in the molecular frame using ab initio LORG calculations. The steric compression at C4 in phenanthrene and in corresponding positions in triphenylene is manifested in a sizable upfield shift in the σ33 component relative to the corresponding σ33 values at C1 and C9 in phenanthrene. The upfield shift in σ33 is mainly responsible for the well-known upfield shift of the isotropic chemical shifts of such sterically perturbed carbons. In phenanthrene C9 exhibits a unique σ22 value reflecting the greater localization of π-electrons in the C9-C10 bond. This localization of the π-electrons at the C9-C10 bond in the central ring of phenanthrene also corresponds with the most likely ordering of electrons described by the various Kekule? structures in phenanthrene. The analysis of the 13C chemical shieldings of the bridgehead carbons in triphenylene provides significant experimental information on bonding between rings in polycyclic aromatic compounds. The results confirm that the electronic structure of triphenylene is best described by three fairly isolated benzene rings linked by C-C bonds of essentially single bond character. Similarly in phenanthrene, the bonding structure which correlates the shielding information may be characterized by the dominance of two benzene rings comprising the biphenyl moiety. A strong C9-C10 π-bond with only limited π-electron character in the C8a-C9 and C10-C10a bonds is indicated by both the experimental and theoretical results.
- Soderquist, Arien,Hughes, Craig D.,Horton, W. James,Facelli, Julio C.,Grant, David M.
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- A facile synthesis of 3-(chloromethyl)-2-methyl-1,1'-biphenyl
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3-(Chloromethyl)-2-methyl-1,1′-biphenyl is a key intermediate for the preparation of bifenthrin, an insecticide which belongs to pyrethroid. The traditional synthetic process of 3-(chloromethyl)-2-methyl-1,1′-biphenyl is complicated and involves high-toxic and high-risk reagents such as thionyl chloride, lithium aluminum hydride and methyl iodide, which causes significant environmental problems and safety issues. Herein, a facile and efficient synthesis process of 3-(chloromethyl)-2- methyl-1,1′-biphenyl was developed. The synthetic process is shortened from 6 steps to only 4 steps and avoids the use of high-toxic and high-risk reagents. Moreover, 3-(chloromethyl)-2-methyl-1,1′-biphenyl can be obtained by simple purification process in high yield (73.9 %). Compared with the traditional synthetic process, the synthetic process of 3-(chloromethyl)-2-methyl-1,1′-biphenyl reported here is more environmental friendly and efficient.
- Zhang, Lele,Cheng, Songbo,Hang,Defeng
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- Binuclear metallocene compound, preparation method and applications thereof
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The invention relates to the field of olefin polymerization, and discloses a binuclear metallocene compound, a preparation method and applications thereof, wherein the binuclear metallocene compound has a structure represented by a formula (1). When the binuclear metallocene compound is applied to olefin polymerization as a catalyst component, good catalytic activity can be effectively provided, and a polyolefin product with improved isotacticity is prepared.
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- Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides
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We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.
- Houle, Camille,Savoie, Paul R.,Davies, Clotilde,Jardel, Damien,Champagne, Pier Alexandre,Bibal, Brigitte,Paquin, Jean-Fran?ois
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supporting information
p. 10620 - 10625
(2020/07/24)
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- Method for preparing N,N-dimethyl-1-alkyl diphenylmethylamine
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The invention discloses a method for preparing N,N-dimethyl-1-alkyl diphenylmethylamine and relates to the field of fine chemical engineering. The method disclosed by the invention comprises the following steps: taking waste alkyl biphenyl recovered in the conventional process as a raw material, carrying out a free radical reaction between the raw material and a halogenating reagent in the presence of a catalyst so as to obtain halogenated alkyl biphenyl; reacting the halogenated alkyl biphenyl and organic alkali to obtain a quaternary ammonium salt; and finally, performing low temperature inversion under liquid ammonia conditions, thereby obtaining N,N-dimethyl-1-(2-methyl-[1,1'-biphenyl]-3-yl) methylamine. Usage of a high-risk reagent lithium aluminum hydride and a strong carcinogen iodomethane can be avoided in the preparation process of the N,N-dimethyl-1-(2-methyl-[1,1'-biphenyl]-3-yl) methylamine, harm to the human body is eliminated, production of three wastes is reduced, the environmental pollution is avoided, and the method is safe and environmental-friendly.
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Paragraph 0042-0046; 0061-0063; 0068-0070
(2019/01/21)
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- Containing 4 - imidazolyl of glutaminyl cyclase inhibitor preparation method and application of (by machine translation)
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The invention discloses a containing 4 - imidazolyl of glutaminyl cyclase inhibitor preparation method and application, wherein the method includes the steps of: in order to has the bromine substituent and R1 B unit of raw materials and with boron acid radical and R2 C unit raw materials of starting, by the Suzuki coupling reaction, preparation B unit and C unit coupled biphenyl intermediate; to B unit and C unit coupled biphenyl intermediate and 2 - (1 H - imidazole - 4 - yl) ethylamine as a raw material, by the SN2 The reaction preparation obtained based on 4 - imidazolyl pharmocology compound. Preparation method of this invention, its only need to Suzuki coupling, SN2 reaction two-step to be completed, the process of the invention route is simple and feasible, high yield, is more suitable for large-scale preparation; and the present invention obtained in the preparation method based on 4 - imidazolyl of glutaminyl cyclase inhibitor has high activity, can be widely used for high-efficiency QC inhibitor the development of new drugs, AD, tumor, rheumatic arthritis QC specific high expression related diseases, early diagnosis and diagnostic kit and the development of. (by machine translation)
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Paragraph 0043; 0045-0047
(2019/02/19)
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- MALONONITRILE OXIME ETHER COMPOUND AND USE THEREOF
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Disclosed is a malononitrile oxime ether compound having a novel structure as shown in the general formula I. Respective substituents in the general formula I as defined in the specification. The compound of the general formula I exhibits an excellent microbicidal activity, and can effectively prevent and treat plant diseases caused by bacteria and fungi. Also provided is a use of the compound of the general formula I as a microbicide in the agricultural and other fields.
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Paragraph 0086; 0087
(2019/01/04)
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- Glutaminyl cyclase inhibitor containing 4-imidazolyl group
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The invention discloses a glutaminyl cyclase inhibitor containing a 4-imidazolyl group. The structural formula of the glutaminyl cyclase inhibitor containing the 4-imidazolyl group is shown in the description. The glutaminyl cyclase inhibitor containing a 4-imidazolyl group is designed according to a crystal structure at the active center of a target enzyme protein, so the structure diversity of amolecular key pharmacophore is further expanded, and the QC inhibition activity is high.
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Paragraph 0034; 0036; 0037; 0038
(2019/01/06)
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- Synthesis of Fluorenes Starting from 2-Iodobiphenyls and CH2Br2 through Palladium-Catalyzed Dual C-C Bond Formation
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A facile and efficient approach is developed for the synthesis of fluorene and its derivatives starting from 2-iodobiphenyls and CH2Br2. A range of fluorene derivatives can be synthesized under relatively mild conditions. The reaction proceeds via a tandem palladium-catalyzed dual C-C bond formation sequence through the key dibenzopalladacyclopentadiene intermediates, which are obtained from 2-iodobiphenyls through palladium-catalyzed C-H activation.
- Shi, Guangfa,Chen, Dushen,Jiang, Hang,Zhang, Yu,Zhang, Yanghui
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p. 2958 - 2961
(2016/07/06)
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- Gold-catalyzed 6-exo-dig cycloisomerization: A versatile approach to functionalized phenanthrenes
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A novel gold-catalyzed 6-exo-dig cycloisomerization of o-propargylbiaryls has been developed that provides ready access to functionalized phenanthrenes in largely good to excellent yields. Notable features of this method are readily available starting materials, mild reaction conditions, and broad substrate scope. Golden cat: A novel gold-catalyzed 6-exo-dig cycloisomerization of o-propargylbiaryls has been developed that provides ready access to functionalized phenanthrenes in largely good to excellent yields. Notable features of this method are readily available starting materials, mild reaction conditions, and broad substrate scope.
- Shu, Chao,Li, Long,Chen, Cheng-Bin,Shen, Hong-Cheng,Ye, Long-Wu
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p. 1525 - 1529
(2014/06/09)
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- A new synthetic approach to 6-unsubstituted phenanthridine and phenanthridine-like compounds under mild and metal-free conditions
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A new and mild synthetic approach for the synthesis of 6-unsubstituted phenanthridine and phenanthridine-like compounds under metal-free conditions at room temperature has been developed. The strategy involved a tandem azide rearrangement/intramolecular annulation and oxidation reactions of biarylmethyl azide precursors to obtain the desired products in up to 99% yields with high regioselectivity.
- Tummatorn, Jumreang,Krajangsri, Suppachai,Norseeda, Krissada,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
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p. 5077 - 5081
(2014/07/08)
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- Process for the preparation of aromatic bromoalkyl-substituted hydrocarbon compounds
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The present invention relates to a process for the preparation of an aromatic bromoalkyl-substituted hydrocarbon compound, in which an alkyl-substituted aromatic hydrocarbon compound is reacted with a brominating agent in the presence of water.
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- MULTICYCLIC TERTIARY AMINE POLYAROMATIC SQUALENE SYNTHASE INHIBITORS
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This invention relates to polycyclic compounds containing two mono- and/or bicyclic rings and a basic tertiary amino group capable of forming an ammonium ion at biological pH and which reduces levels of serum cholesterol in the body without significantly reducing mevalonic metabolite synthesis. This invention relates also to pharmacological compositions and method of treatment for lowering serum cholesterol levels using the compounds of this invention. The compounds of this invention are described by the formula where Ar I is phenylene or naphthylene, Ar II is phenyl or naphthyl and A is 1-azabicyclo[2.2.2]octan-3-yl
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- Phosphono/biaryl substituted dipetide derivatives
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The invention relates to the N-phosphonomethyl-biaryl substituted dipeptide derivatives of formula I STR1 and tetrazole derivatives of the formula Ia STR2 wherein A represents a direct bond, lower alkylene, phenylene or cyclohexylene; m represents 1 or zero, provided that m represents 1 when A is a direct bond; R2 represents hydrogen, hydroxy, lower alkyl, aryl-lower alkyl, C5 -C7 -cycloalkyl-lower alkyl, amino-lower alkyl, hydroxy-lower alkyl, lower alkylthio-lower alkyl, lower alkoxy-lower alkyl, aryl-lower alkylthio-lower alkyl or aryl-lower alkoxy-lower alkyl; biaryl represents phenyl substituted by carbocyclic or heterocyclic aryl; and pharmaceutically acceptable mono-, di- or tri-ester derivatives thereof in which one, two or three of the acidic hydroxy groups of the carboxyl and/or phosphono functional groups are esterified in form of a mono-, di- or tri-pharmaceutically acceptable ester; and pharmaceutically acceptable amide derivatives thereof wherein the carboxyl group is derivatized in form of a pharmaceutically acceptable amide; and pharmaceutically acceptable salts thereof; pharmaceutical compositions comprising said compounds; methods for the preparation of said compounds and for the preparation of intermediates; and methods of treating disorders in mammals which are responsive to the inhibition of neutral endopeptidases by administration of said compounds to mammals in need of such treatment.
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- Phosphono/biaryl substituted dipeptide derivatives
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The invention relates to the N-phosphonomethyl-biaryl substituted dipeptide derivatives of formula I STR1 wherein A represents a direct bond, lower alkylene, phenylene or cyclohexylene; m represents 1 or zero, provided that m represents 1 when A is a direct bond; R2 represents hydrogen, hydroxy, lower alkyl, aryl-lower alkyl, C5 -C7 -cycloalkyl-lower alkyl, amino-lower alkyl, hydroxyl-lower alkyl, lower alkylthio-lower alkyl, lower alkoxy-lower alkyl, aryl-lower alkylthio-lower alkyl or aryl-lower alkoxy-lower alkyl; biaryl represents phenyl substituted by carbocyclic or heterocyclic aryl; and pharmaceutically acceptable mono-, di- or tri-ester derivatives thereof in which one, two or three of the acidic hydroxy groups of the carboxyl and phosphono functional groups are esterified in form of a mono-, di- or tri- pharmaceutically acceptable ester; and pharmaceutically acceptable amide derivatives thereof wherein the carboxyl group is derivatized in form of a pharmaceutically acceptable amide; and pharmaceutically acceptable salts thereof; pharmaceutical compositions comprising said compounds; methods for the preparation of said compounds and for the preparation of intermediates; and methods of treating disorders in mammals which are responsive to the inhibition of neutral endopeptidases by administration of said compounds to mammals in need of such treatment.
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- 4-Phenyl-2-indanyl esters of 1R,cis-3-(2-halo-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylic acid
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Insecticidal 4-phenyl-2-indanyl 1R,cis-3-(2-halo-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates having a racemic or optically active indanyl moiety, methods of preparation and use, and efficacy data against representative insect species are disclosed and exemplified.
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- Solid-State Chemistry, Kinetics, and Electron Spin Resonance Spectroscopy of 2-Biphenylmethylene
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The chemistry and kinetics of 2-biphenylmethylene have been examined in low-temperature glasses and polycrystals.Photolysis of 2-biphenyldiazomethane at 77 K produces a single set of triplet carbene resonance peaks.They have been assigned to the unresolved superposition of syn and anti rotamers of the carbene.The carbene kinetics are fastest in diethyl ether glass.The decay rates of 4T in diethyl-d10 ether and in a perfluorinated alkane polycrystal are comparable.This indicated that the main carbene reaction in diethyl ether is hydrogen atom abstraction.The reaction of 4T in diethyl-d10 ether is a mixture of reaction with solvent and cyclization to fluorene.These interpretations are consistent with the observed product distributions.Matrix effects on the observed chemistry are discussed.
- Palik, Eric C.,Platz, Matthew S.
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p. 963 - 969
(2007/10/02)
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- Insecticidal pyrethroid enantiomer pair
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An insecticidal enantiomer pair consisting essentially of a substantially equimolar mixture of S-4-phenyl-2-indanyl 1R, cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate and R-4-phenyl-2-indanyl 1S,cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, its preparation by liquid chromatography, and its utility as an insecticide are described and exemplified.
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- 4-Substituted-2-indanols
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Novel compounds of the formula STR1 are disclosed in which R1 is a phenyl, phenoxy, phenylthio, benzyl or heterocyclic radical which may be substituted, and R2 is hydrogen. The compounds are intermediates of cyclopropanecarboxylate and related insecticides.
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- Intraanular phenyl-substituierte Phane - Synthese und dynamische Stereochemie
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The synthesis and properties of phanes of different ring size, substituted intraanularly by phenyl groups, and of new biphenylophanes 3, 38 - 43 with "pseudo-syn/anti"-structure are described.Barriers for the hindered rotation of intraanular phenyl substituents have been determined by D-NMR spectroscopy. syn/anti conformers of -, -, - and metacyclophanes are found.A better method for the preparation of mediocyclic bisdisulfides is reported.The pyrolysis of (2-biphenylyl)methyl sulfones leads to fluorenes; pyrolysis of the thiosulfonic S-ester 44 yields bibenzyl and dibenzyl sulfide.
- Boeckmann, Klaus,Voegtle, Fritz
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p. 1048 - 1064
(2007/10/02)
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- 4-Substituted-2-indanol insecticidal ester derivatives
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Novel compounds of the formula STR1 are disclosed in which R1 is a phenyl, phenoxy, phenylthio, benzyl or heterocyclic radical which may be substituted, and R2 is hydrogen, a substituted-vinylcyclopropanecarbonyl group, a tetramethylcyclopropanecarbonyl group, or a 1-(substituted-phenyl)-2-methylpropylcarbonyl group. The compounds wherein R2 is other than hydrogen are insecticides.
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