Facile synthesis of fluorine containing imidazo [1,2-b] [1,2,4] triazines through α-oxo-n-aryl-α arylethanehydrazonoyl bromides

Treatment of fluorine containing arylglyoxals with aminoguanidine bicarbonate in aqueous ethanol formed fluorinated 3-amino-5-aryltriazines which in turn ontreatment with α-oxo-N-aryl-α-arylethanehydrazonoyl bromides afforded 3,6-diaryl-7-arylazoimidazo[1,2-b][1,2,4] triazines in 75–80% yield. All the compounds were characterized by their analytical and spectral (IR, PMR and Mass) data. Mass fragmentation patterns of these compounds have also been discussed. The screening of biological activities are in progress.     

Fluorine in health care: Organofluorine containing blockbuster drugs

Organic fluorine compounds have had a profound impact on the development of bioactives for the modern pharmaceuticals market. It is estimated that up to 20% of pharmaceuticals prescribed or administered in the clinic contain a fluorine atom and 30% of the leading 30 blockbuster drugs by sales contain a fluorine. In this Highlight review, the top 10 fluorine containing pharmaceuticals (by US Sales in 2008) are highlighted. By this measure, these are currently the most significant fluorinated compounds impacting on health care. They embrace statins (Lipitor, Crestor, Vytorin, Zetia/Ezetimibe), anti-inflammatories (fluticasone propionate, Celebrex), antacids (Prevacid), antidepressants (Lexapro), neuroleptics (Risperdal) and antibiotics (Levaquin). In each case the structures and modes of action of these important drugs compounds are reviewed and representative synthetic routes are highlighted.     

Effect of lateral substitution by fluorine and bromine atoms in ferroelectric liquid crystalline materials containing a 2-alkoxypropanoate unit

Two homologous series of ferroelectric liquid crystalline compounds with 2-alkoxypropanoate chiral unit containing biphenyl benzoate core laterally substituted by fluorine and bromine have been synthesized and studied. All compounds possess the ferroelectric smectic C* phase over a broad temperature range. For bromine-substituted compounds values of spontaneous polarization reach high values up to 250 nC cm^-2. The effects of the lateral substitution on the phenyl ring far from the chiral centre by methyl and methoxy groups, fluorine, chlorine and bromine atoms on mesomorphic properties and on values of the spontaneous polarization are discussed.     

Effect of lateral substitution by fluorine and bromine atoms in ferroelectric liquid crystalline materials containing a 2‐alkoxypropanoate unit

Two homologous series of ferroelectric liquid crystalline compounds with 2‐alkoxypropanoate chiral unit containing biphenyl benzoate core laterally substituted by fluorine and bromine have been synthesized and studied. All compounds possess the ferroelectric smectic C* phase over a broad temperature range. For bromine‐substituted compounds values of spontaneous polarization reach high values up to 250 nC cm^?2. The effects of the lateral substitution on the phenyl ring far from the chiral centre by methyl and methoxy groups, fluorine, chlorine and bromine atoms on mesomorphic properties and on values of the spontaneous polarization are discussed.     

Syntheses of 4-methoxymethylbenzyl permethrinates containing fluorine and their insecticidal activity

In order to investigate the relationship between the position of fluorine atom and insecticidal activity about 4-methoxymethylbenzyl permethrinates containing fluorine, 2 and 3-fluoro-4-methoxymethylbenzyl (±)-cis-permethrinate were synthesized. Their insecticidal activities were tested and the fluorine effect of title compounds was discussed.     

Molecular structure investigations on fluorine containing polyazomethines by means of the MALDI-TOF-MS technique

Three new aromatic polyazomethines have been synthesized by solution polycondensation reactions of terephthalic dialdehyde with fluorine containing aromatic diamines. The polymers were obtained in high yields. The investigation of these polymers by means of matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry (MALDI-TOF-MS) proved the initial members of the four theoretical possible series of the corresponding oligomers with 2-10 repeating units per molecule.     

1,4-氧硫杂萘-4,4-二氧化物含氟衍生物的合成

以含氟的2-(2-氯-4-硝基苯磺酰基)-1-劳基乙酮为原料,在K_OCO_3/TEBA/DMF体系中,与烷基化试剂发生烷基化-环化反应。合成六种未经文献报道的1,4-氧硫杂萘-4,4-二氧化物的含氟衍生物,利用元素分析、IR、~1H NMR、MS对其结构进行了表征。     

含氟新农药的构效关系研究Ⅰ.经典QSAR分析

为了能更深入地认识含氟新化合物作为农药的生物活性和其结构间的关系,建立有意义的构效关系模型,我们用经典QSAR(定量构效关系)方法研究了三十三个含氟化合物的两种不同的生物活性与结构的关系,其对抗黄瓜疫病活性模型有很好的解释能力和预测能力,并根据这个模型设计了一些新的活性结构.而对抑制西瓜白绢病的活性数据的处理未能获得理想模型.通过这一工作确立了先应用聚类等定性分析方法,再用多元统计分析方法作更深入研究的QSAR研究模式.     

Modified Silica Sol Coatings for Water-Repellent Textiles

The preparation of water repellent textiles by coating with different modified silica sols has been investigated. For this, pure and with 3-glycidoxypropyl triethoxysilane co-condensed silica sols were modified by three types of additives: alkyltrialkoxysilanes, polysiloxane derivatives and a fluorine containing silane. Hydrophobic properties of the coated fabrics of polyamide and of polyester mixed with cotton were determined using contact angle measurements. The hydrophobicity increases with increasing concentration of the alkylsilane additive in the silica sol and the length of the alkyl chain but with high additive concentrations plateau values in hydrophobicity were reached. Analogously textile coatings with high hydrophobicity were gained using hydrophobic polysiloxane or fluorine containing silicon compounds. The comparison of the different variants reveals that high wash-out stabilities were reached only by silica sols containing fluorine compoundsand hexadecylsilane additives. Therefore long-chain alkyltrialkoxysilane compounds could be used as substitutes for fluorine compounds for the surface modification of textiles in some practical applications.     

Determination of oxygen,fluorine and boron by 14-MeV INAA: A case of multiple interferences

Oxygen and fluorine have been simultaneously determined by 14-MeV INAA in samples containing boron. Both boron and fluorine can cause serious interferences in the determination of oxygen. The fluorine and boron interference corrections for oxygen determination have been determined to be 0.43±0.01 and 0.0832±0.0017 apparent g oxygen per g of fluorine and boron, respectively, for our system. Boron can be determined in the same sample by a second irradiation. Mutual interferences have been evaluated and the procedure has been applied to NIST SRM and several other compounds.     

Microwave‐assisted Three‐component Reactions for Regioselective Synthesis of Functionalized Benzo[e]indoles

Microwave‐assisted three‐component reactions of arylglyoxals with cyclic 1,3‐dicarbonyl compounds and naphthalen‐2‐amine have been established, by which a series of new functionalized benzo[e ]indoles with good yields were synthesized. The reaction was easily conducted in HOAc, enabling domino cyclization to construct three new σ‐bonds in a one‐pot operation. Flexible structural modification and broad functional group compatibility as well as mild reaction conditions make this strategy a useful and attractive process of library generation for drug discovery.     

Synthesis and herbicidal activity of O,O-dialkyl phenoxyacetoxyalkylphosphonates containing fluorine

A series of substituted phenoxyacetoxyalkylphosphonates bearing fluorine were designed and synthesized. All the new compounds were identified by elemental analysis, IR, ¹H NMR and MS and were tested for herbicidal activity in greenhouse at a rate of 1.5 kg/ha. The results of preliminary bioassay showed that fluorine moiety introduced to the core structure could help to improve the herbicidal activity, and compounds with a 3-trifluoromethyl in benzene ring exhibited higher inhibitory activity.     

含呋喃环Schiff碱型大环化合物的合成及其与Ba^2+,Sr^2+配合行为

利用Mn^2+，Ba^2+及Sr^2+作为模板离子，合成了一类新型的含呋喃环系 Schiff碱型大环化合物，如L^1和配合物L^2Ba(ClO4)2，L^3Ba(ClO4)2和L^4Ba (ClO4)2.L^2-L^4的Ba^2+配合物经与NaSO4水溶液反应解络，得到自由配体L^2， L^3和L^4，配体L^2和L^3分别与Sr^2+作用，得到配合物L^2Sr(ClO4)2和L^3Sr (ClO4)2。上述大环配体和各种配合物均经元素分析，IR，^1H NMR，MS等证实了它 们的结构和组成。     

Prototropic processes in benzaurins. <Superscript>19</Superscript>F and <Superscript>1</Superscript>H NMR spectra of fluoro- and methylsubstituted 4-hydroxyphenyl-diphenylcarbinols,related fuchsones and benzaurins

Tautomerism of benzaurins and hydration are studied. ¹H and ¹⁹F chemical shifts have been determined for a number of substituted 4-hydroxyphenyl-diphenyl carbinols containing fluorine in a 3-, 3*- or 4*-position, and for similar compounds containing additional methyl groups in a position of 3, 3** or 4**. The same data have been obtained for the fuchsones prepared by dehydration of the above carbinols. On this basis chemical shifts of fluorine in different positions have been evaluated as a monitor of the transformation of 4-hydroxyphenyl group to the semiquinone moiety. The ¹⁹F NMR can be used to monitor the transformation of 4**-fluorobenzaurin and the related 3,3*-disubstituted and 3,3*,5,5*-tetramethylsubstituted compounds to the corresponding carbinols due to the addition of a water molecule and to study the tautomerism of the two latter benzaurins as well as that of 3,3*,4**trifluorobenzaurin. Furthermore, fluorine and methyl group chemical shifts are sensitive to syn-anti-isomerism in substituted fuchsones.     

Synthetic applications of electrophilic fluorodesilylation

Recently, with the appearance of electrophilic sources of fluorine including the commercially available N-F reagents, the concept of electrophilic fluorodesilylation has emerged as a new strategy to prepare a variety of fluorine containing compounds. This paper highlights how this concept has been applied to the preparation of a series of fluorinated molecules including fluoroaromatic compounds, fluoroalkenes, difluoroamides, difluoroalcohols, difluoroethers and alpha-fluorinated carbonyl derivatives.     

含氟新农药的构效关系研究Ⅱ.三维定量构效关系分析

为了能更深入地认识含氟新化合物作为农药的生物活性和其结构间的关系,建立有意义的药物-受体作用模型,寻找同类化合物的药效团,对合成的含氟化合物在经典QSAR方法研究的基础上,又进一步运用DISCO,CoMFA和Leapfrog方法研究了它们的三维构效关系.首先根据化学结构,将分子进行了分类,然后再分别进行CoMFA计算,根据第I类分子的CoMFA结果,我们进行了含氯化合物的全新设计.根据各类中较好的构效关系模型,我们进行了分子的改造,预测了它们的活性.     

氟代有机硅化合物的合成新方法

本工作利用CuCl/HOC₂H₄NH₂催化剂,将1,2-二溴四氟乙烷与烯基有机硅化合物进行加威反应,制备了一系列新的含氟有机硅化合物,并进行了分析鉴定。对影响反应的诸因素做了初步探讨。     

A step toward direct fullerene synthesis: C60 fullerene precursors with fluorine in key positions

Several fluorine containing polycyclic aromatic hydrocarbons with exact carbon atom topology of the C₆₀ fullerene have been synthesized. Different numbers of fluorine atoms were introduced in the key positions, as needed for an efficient intramolecular condensation to the fullerene molecule. The polycyclic aromatic compounds obtained represent attractive precursors for rational, high-yield fullerene synthesis by flash vacuum pyrolysis.     

Synthesis and structure-insecticidal activity relationship of novel phenylpyrazole carboxylic acid derivatives containing fluorine moiety

A series of novel phenylpyrazole carboxylic acid derivatives containing fluorine moiety,i.e.,diamides 11,simple aryl-bearing amides 12 and acylthioureas 14 were successfully synthesized based on the key fluo ro-containing phe nylpyrazole acid intermediate.The new compounds were identified and confirmed by melting point,1H NMR,13C NMR and elemental analysis or HRMS.The bioassay results indicated that some of the compounds possessed excellent insecticidal activities towards oriental armyworm,diamondback moth and corn borer at low concentrations.For examples,compounds 11a,11e-g and 14b exhibited remarkable larvicidal activities with LC50 values of 0.13-0.39 mg/L and 0.0002-0.0014 mg/L against oriental armyworm and diamondback moth,respectively,were comparable with those of the control chlorantraniliprole.Particularly,lie were found superior to chlorantraniliprole in oriental armyworm tests(LC50:0.23 mg/L vs.0.26 mg/L);11a,lie,11f and 14c in diamondback moth tests with LC50 values of 0.0002 mg/L,0.0002 mg/L,0.0008 mg/L and 0.0005 mg/L,respectively,we re more effective than that of chlorantraniliprole.In addition,12 a also showed a promising insecticidal potential and development/optimization advantage.Compounds 11a,lle-g,12a,14b and 14c could be considered as possible new leading structures for further study.The SAR investigation indicated that the compounds with fluorine motif(e.g.,-F,-CF2H,-CF3)held apparently favorable insecticidal potentials,which provided useful guidance for further design/development of new phenylpyrazole-containing agrochemicals.     

Regioselective hydrosilations. IV. The synthesis and polymerization of monomers containing epoxy and alkoxysilane groups

Using rhodium and platinum catalyzed regioselective hydrosilation, a series of α-hydrogen-ω-epoxy silane and siloxane compounds have been prepared in good yields. These intermediates have been further condensed with vinyltrimethoxysilane in subsequent hydrosilation reactions to prepare an interesting new class of ambifunctional monomers containing both epoxy and trimethoxysilane groups. It was further shown that these same compounds could be synthesized by a simplified “one-pot” two-step procedure. An investigation of the simultaneous cationic ring-opening polymerization of the epoxy groups and the acid-catalyzed condensation of the trimethoxysilyl groups was carried out. © 1993 John Wiley & Sons, Inc.