一种新型含氟菊酸的合成

本文以４－甲基－３－戊烯－２－酮为原料，经三步反应，合成了一种新型的拟除虫菊酯中间体反－３－（１－甲基－２，２－二氟乙烯基）－２，２－二甲基环丙烷羧酸，总产率为５０．０％。     

混合含氟甲苄醇类菊酯的结构与杀虫活性关系

报道了混合含氟甲苄醇类菊酯对库蚊和家蝇的生物测试。其结果表明该类化合物对测试害虫显示出较高的杀虫活性和较低的抗性比。在抗性品系中，混合含氟甲苄醇类菊酯表现出比单一异构体和氯氰菊酯更高的活性。     

偏氯菊酸对甲氧基苄酯的合成研究

报道了一种新的拟除虫菊酯——偏氯菊酯的合成方法.以贲亭酸甲酯为原料,氯化亚铁作为引发剂在密闭体系中与氯仿加成后得到3,3-二甲基-4,6,6-三氯己酸甲酯,再成环、脱卤化氢,水解酸化后得到2,2-二甲基-3-(乙氯乙烯基)-环丙烷羧酸(偏氯菊酸),偏氯菊酸钠与季铵盐回流得到标题化合物.在合成中得到了3种未见文献报道的新...     

偏氯代含氟氰菊酯的生物活性研究

偏氯菊酸α-氰基-4-氟-3-苯氧基苄酯是一类新型拟除虫菊酯。它对淡色库蚊幼虫的相对杀死毒力是溴氰菊酯的2.3～10.5倍;对农业中的三大类典型害虫(粘虫、蚜虫、螨虫)的平均杀死率分别为66.7%(1mg/L),84.3%(1mg/L)和91%(50mg/L),表现出高杀死活性;对大鼠急性经口毒性分别为LD50=116.5mg/kg(雄性)和158mg/kg(雌性)。     

手性试剂(R)-β-甲基-γ-丁内酯及其衍生物的合成

以剑麻皂甙元为原料,经氧化降解得到了手性目标化合物.再与溴化氢/无水乙醇反应,以86%的收率得到(R)-4-溴-3-甲基丁酸乙酯;当目标化合物与苄溴/氢氧化钠反应时,可选择性地分别以91%和90%的收率得到(R)-4-苄氧基-3-甲基丁酸和(R)-4-苄氧基-3-甲基丁酸苄酯.合成产物的结构采用IR、~1HNMR和MS等确认.它们不仅为药物和生物活性天然化合物的合成提供了新的合成中间体,也为它们的新合成途径设计提供了机遇.     

3，3-二甲基-4-戊烯酸-3′-甲基-2′-丁烯酯的回收与利用

针对目前工业上回收3，3-二甲基-4-戊烯酸-3′-甲基-2′-丁烯酯（MBDP）工艺复杂、异戊烯大量分解问题，研究了MBDP直接返回循环使用工艺，MBDP与甲醇、原乙酸三甲酯或与甲醇原乙酸三甲酯混合溶液进行酯交换反应的回收新工艺，比较了四异丙基钛酸酯、甲醇钠、氢氧化钾用作酯交换催化剂的效果，筛选出回收MBDP“一锅煮”最佳工艺：按照n（MBDP）：n（原乙酸三甲酯）：n（甲醇）：n（甲醇钠）=1．0：9．8：9．2：0．05物质的量比投料，74℃-78℃反应2lh，MBDP转化为贲亭酸甲酯和异戊烯醇，单程转化率87．7％，用85％的磷酸中和甲醇钠，蒸出甲醇，直接用于合成贲亭酸甲酯。     

3,3-二甲基-4-戊烯酸-3''''-甲基-2''''-丁烯酯的回收与利用

针对目前工业上回收3,3-二甲基-4-戊烯酸-3'-甲基-2'-丁烯酯(MBDP)工艺复杂、异戊烯大量分解问题,研究了MBDP直接返回循环使用工艺,MBDP与甲醇、原乙酸三甲酯或与甲醇原乙酸三甲酯混合溶液进行酯交换反应的回收新工艺,比较了四异丙基钛酸酯、甲醇钠、氢氧化钾用作酯交换催化剂的效果,筛选出回收MBDP“一锅煮”最佳工艺:按照n(MBDP)∶n(原乙酸三甲酯)∶n(甲醇)∶n(甲醇钠)=1.0∶9.8∶9.2∶0.05物质的量比投料,74℃～78℃反应21h,MBDP转化为贲亭酸甲酯和异戊烯醇,单程转化率87.7%,用85%的磷酸中和甲醇钠,蒸出甲醇,直接用于合成贲亭酸甲酯。     

有杀虫活性的取代的3—甲基—2—2苯氧基丁酸五氟苄酯的合成

合成拟除虫菊酯因其杀虫活性高、对哺乳动物毒而被认为具有是广阔前景的杀虫剂。２－溴－３－甲基丁酸与对位上分别有Ｆ、ＣＬ、Ｂｒ、ＯＣＨ３和ＣＦ３的苯酚反应制得有不同取代基的３－甲基－２－苯氧基丁酸。这些酸的氯化物与五氟苄醇反应得五种除拟虫菊酯,其中在酸部分的苯环上分别含Ｆ、ＣＬ、Ｂｒ、ＯＣＨ３取代基的种化合物Ⅰ、Ⅱ、Ⅲ、Ⅳ对五带淡色谈蚊（Ｃｕｌｅｘｑｕｎｑｕｅｆａｓｃｉａｔｕｓ）具明显的杀虫活性,对幼     

5-苄氧基-2-(4-苄氧基苯基)-3-甲基-1H-吲哚的合成研究

以4-硝基苯酚、1-(4-羟基苯基)-1-丙酮为起始原料,经过羟基保护、还原、溴代、BischlerM觟hlau吲哚合成法等反应合成了5-苄氧基-2-(4-苄氧基苯基)-3-甲基-1H-吲哚。该路线原料廉价易得、操作简单、副反应少,收率接近50%,具有较好的应用前景。     

Synthesis and application of fluorine containing graftcopolymers

Summary Well-defined graftcopolymers were prepared by radical copolymerization of methyl methacrylate macromonomer with perfluoroalkyl acrylate. Contact angle of the solvent cast films of poly(methyl methacrylate) containing various amount of the graftcopolymer was measured against water droplet. Addition of 0.2 wt% of the graftcopolymer was sufficient to improve the polymer films to water repellent surfaces, while 10 wt% was necessary to modify the polymer surfaces to the same level of water repellency.     

甲苄基不对称三甲川菁染料的合成及光谱性能

以对肼基苯磺酸和3-甲基-2-丁酮为原料经催化合成2,3,3-三甲基-3H-吲哚-5-磺酸,进一步制得钾盐。经钾盐合成N-甲苄基取代吲哚季铵盐。采用一步法将钾盐与吲哚季铵盐缩合为一种不对称三甲川菁染料,并考查其光谱性能。所合成染料经C-18反相柱分离提纯,利用核磁共振氢谱进行了结构表征。     

Synthesis and characterization of fluorine and nitrile containing polyimides

A series of polyimides were synthesized from new diamine, Bis [4,4′‐amino‐5,5′ trifluoromethyl phenoxy‐(hexafluoro isopropylidine) phenoxy phenyl] benzonitrile [BATFB] and various aromatic tetracarboxylic anhydrides by thermal and chemical imidization routes. The BATFB was synthesized in two steps by nucleophilic displacement reaction of 2,6‐dichloro benzonitrile, 4,4′‐(hexafluoro isopropylidine) diphenol and 2‐amino‐5‐fluoro benzotrifluoride in the presence of anhydrous potassium carbonate in N,N′‐dimethyl acetamide (DMAc) and the structure was confirmed by FTIR spectroscopy and CHNSO analyzer. The polymers were characterized by FTIR spectroscopy and thermal analysis were performed by differential scanning calorimetry and thermogravimetric analysis methods. The prepared polyimides had glass transition temperatures between 230 and 290°C and their 10% weight loss were recorded in the range 550–590°C in N₂ atmosphere. Majority of polymers are found to be soluble in most of the organic solvents such as DMSO, DMF, DMAc, m‐cresol, and THF even at room temperature and few becomes soluble on heating. The prepared polyimides showed water uptake values 0.34–0.54 wt % at room temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3455–3461, 2006     

相转移催化合成N,N-二乙基氨基乙基-4-甲基苄基醚

以二乙氨基乙醇和对甲基氯化苄为原料,以四丁基溴化铵为相转移催化剂,合成了N,N－二乙基氨基乙基－4－甲基苄基醚,产率最高可达87．78％。考察了催化剂、温度、反应时间以及氢氧化钠用量对反应的影响,确定了最佳反应条件。产物经过沸点、折光率、红外光谱、氢质子核磁共振谱认证。     

Synthesis,characterization, and properties of novel fluorine containing aromatic polyamides

A series of novel fluorine containing aromatic polyamides were synthesized by the direct polycondensation of various fluorine containing aromatic diamines and commercially available 5‐t‐butyl isophthalic acid. These polyamides have good solubility in several organic solvents such as dimethylformamide, N,N‐dimethylacetamide, 1‐Methyl‐2‐pyrrolidone, dimethyl sulfoxide, and tetrahydrofuran. The synthesized polymers exhibited inherent viscosities up to 0.93 dL/g and M_w up to 1,52,000 with PDI of 2.49. The polyamides exhibited good thermal stability up to 489°C for 10% weight loss in nitrogen and high glass transition temperature up to 273°C. Dynamic mechanical analysis showed a very good retention of storage modulus up to the glass transition temperature. The tan δ peak value at 1 Hz was used to calculate the T_g and these values are in good agreement with differential scanning calorimetry data. The polyamide films were flexible with tensile strength up to 72 MPa, elongations at break up to 14%, and modulus of elasticity up to 1.39 GPa depending on the exact repeating unit structure. X‐ray diffraction measurements indicate that these polyamides are semicrystalline. Rheology study showed same trend of melt viscosity behavior with different shear rate for all polymers. Water absorption study indicates the hydrophobic nature of the polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of novel macromonomers with polyether possessing fluorine and their polymerization

Novel styrene-type and methacrylate (MA)-type macromonomers with polyether(poly(oxytetramethylene)) possessing a fluorobutyl terminal group were synthesized by the reaction between 4-aminostyrene or 2-hydroxyethyl methacrylate and polyether with a fluoroformyl group at one chain end (prepolymer), which was prepared by the ring-opening polymerization of THF with hexafluoropropylene oxide (HFPO) as an initiator. Macromonomers were easily prepared by mixing a solution containing the prepolymer with 4-aminostyrene or 2-hydroxyethyl methacrylate for several minutes at room temperature. The obtained macromonomers can polymerize with either radical or anionic initiator to afford polystyrene or poly(MA) with polyether grafted segment in each monomer unit.     

Synthesis and characterization of UV‐curable acrylic resin containing fluorine groups

A novel fluorine‐containing acrylic resin, 4‐trifluoromethylphenyl glycerol dimethacrylate (TPGD), was synthesized and the structure was characterized by FTIR, ¹³C NMR, ¹H NMR, and ¹⁹F NMR spectroscopy. The conversion of cure reaction, thermal stability, glass transition temperature (T_g), and electrical properties of the TPGD acrylic resin cured with UV radiation were investigated. The thermal stability and T_g of the UV‐cured specimens show a maximum value at 1 wt% photoinitiator, due to the formation of advanced network structures. The cured specimens had a relatively low dielectric constant, attributed to the decreased deformation polarizability of segment motion in the fluorine‐containing resin. Copyright © 2004 Society of Chemical Industry     

Synthesis of copolyimide containing fluorine and naphthalene with synergizing effect on dielectric constants

Summary Novel copolyimides containing fluorine and naphthalene groups were synthesized from 4,4-(Hexafluoroisopropylidene)diphthalic dianhydride (6FDA) and two diamines, 1,4-Bis(4-amino-2-trifluoromethylphenoxy) benzene (BATB) and 2,7-bis(4-aminophenoxy) naphthalene (BAPN) in various ratios via thermal imidization. The introduction of fluorinated groups into dianhydride improved transparency of copolyimides. All films are transparent. The structures and physical properties of copolyimides were characterized by FT-IR, DSC, TGA, XRD, UV-Vis and dielectric analyzer to study the effect of diamines on the physical properties of modified polymers. Copolyimides containing a higher percentage of BAPN have higher glass transition temperature and are less soluble in organic solvents. The copolyimide consisting of 50/50 mole% of BATB/BAPN has the lowest dielectric constant (2.60 at 1 KHz), reflecting the synergizing effect from both diamines.     

9,9-二(4-氨基苯基)芴的合成研究

9,9-二(4-氨基苯基)芴是一种高质量电子发光材料聚酰亚胺的重要中间体。以芴、四氯化碳及苯胺为原料,采用两步法合成了目标化合物,探讨了反应温度、时间等因素对反应的影响。在优化的反应条件下,产品收率达65%,纯度高达99.6%。该合成方法经济,适合工业化生产。     

Synthesis of new fluorine containing ring-opened polynorbornene dicarboximides using ruthenium alkylidene catalysts

Summary  The synthesis of new N-4-trifluoromethylphenyl-exo-endo-norbornene-5,6-dicarboximide (TFmNDI, 2a) and N-3,5-difluorophenyl-exo-endo-norbornene-5,6-dicarboximide (DFNDI, 2b) was carried out. Polynorbornene dicarboximides, 3a and 3b, were obtained via ring opening metathesis polymerization (ROMP) using bis(tricyclohexylphosphine) benzylidene ruthenium(IV) dichloride (I) and tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (II), respectively. T_g’s for polymers 3a and 3b were observed at 155 C and 142 C, respectively. Compared to polymer 3b, polymer 3a with the bulky trifluoromethyl group showed the highest glass transition temperature and improved mechanical properties.