季胺盐型表面活性剂与镉试剂显色反应的研究及应用

在三乙醇胺存在下，季铵盐型表面活性剂溴化十六烷基三甲铵，溴化十二烷基二甲基苄铵和溴化十六烷基吡啶分别与１－（４－硝基苯基）－３－「４－苯基偶氮）苯基」－三氮烯形成离子缔合物显色，吸收光谱红移，离子缔合物；ＮＰ－ＰＡＰＴ与ＤＤＭＢＡＢ来１：２与ＣＴＭＡＢ，ＣＰＢ均为１：３；测定了显色体系的ＣＴＭＡＢ，ＤＤＭＢＡＭ，ＣＰＢ的临界胶束浓度，符合比尔定律的范围，表观摩尔吸光系数δｍａｘ，探讨了微量ＣＴＭＡ     

An effective new access to ethyl 2-[(alkylamino)(cyano)methyl] acrylates: first synthesis of ethyl 3-cyano-2-(hydroxymethyl) acrylate

A regioselective coupling of ethyl 2-(bromomethyl)-3-cyanoacrylate and primary amines is described to give ethyl 2-[(alkylamino)(cyano)methyl] acrylates in good yields. Whereas the conversion of allyl bromide in the presence of TEAF leads to the first synthesis of ethyl 3-cyano-2-(hydroxymethyl) acrylate.     

Synthesis and bioactivity of novel (3-chloro-5-(trifluoromethyl)pyridin-2-yloxy)phenyl containing acrylate and acrylonitrile derivatives

Fifteen novel (3-chloro-5-(trifluoromethyl)pyridin-2-yloxy)phenyl containing Baylis-Hillman adduct derivatives were designed and synthesized. Evaluation of their biological activities showed that methyl 2-((3-(3-chloro-5-(trifluoromethyl)pyridin-2-yloxy)phenoxy)(phenyl)methyl)acrylate (2g) exhibited efficient broad-spectrum fungicidal activity, with 100% control of wheat powdery mildew and cucumber downy mildew and 98% control of cucumber anthracnose at 400 g ai/ha. Some of the other title compounds 2, 3 and two Baylis-Hillman bromide intermediates (11a, 11b) had moderate to good fungicidal activity.     

A versatile synthesis of poly(lauryl acrylate) using N-(n-octyl)-2-pyridylmethanimine in copper mediated living radical polymerization

A facile synthesis of poly(lauryl acrylate) has been achieved by atom transfer radical polymerization using benzyl-2-bromoisobutyrate, copper (I) bromide, and N-(n-octyl)-2-pyridylmethanimine (OPMI). The latter was of great interest as its synthesis was very easy to carry out and as it allowed the reaction mixture to be homogeneous, which was essential for the control of the reaction. The polymerization was controlled under these conditions and was optimized with the addition of copper (II) bromide as deactivator. We proved that the synthesis of poly(lauryl acrylates) with well defined molecular weights and narrow polydispersities was possible using a ligand which does not require difficult synthesis and purification. We also showed the ability of pyridylmethanimine ligands to control ATRP of an acrylate derivative. Best results were obtained at 130 °C in xylene for [Initiator]₀/[Cu(I)Br]₀/[Cu(II)Br₂]₀/[OPMI]/[lauryl acrylate] equal to 1/1/0.05/2.2/181, respectively (M_n = 19,942, DPI = 1.28).     

Phosphonioethylation of phenylhydrazine and hydroxylamine and selected properties of the resulting derivatives

The reactions of phenylhydrazine and hydroxylamine with (-X-ethyl)triphenylphosphonium salts (X = Ph, Ph₃P⁺Br^–) (1, 2) afforded the corresponding -N-ethyl-substituted triphenylphosphonium salts (3, 4). The reaction of triphenyl(2-phenylhydrazinoethyl)phosphonium bromide 3with an aqueous solution of NaOH in benzene afforded a statistical mixture of the nisand transisomers of 2-(diphenylphosphoryl)acetaldehyde phenylhydrazone. (2-Hydroxyaminoethyl)triphenylphosphonium bromide reacted with sodium methoxide to give O-phosphobetaine.     

Novel molecularly imprinted polymer using 1-(α-methyl acrylate)-3-methylimidazolium bromide as functional monomer for simultaneous extraction and determination of water-soluble acid dyes in wastewater and soft drink by solid phase extraction and high performance liquid chromatography

Novel water-compatible molecularly imprinted polymers were synthesized in methanol-water systems with Tratarzine as template and 1-(α-methyl acrylate)-3-methylimidazolium bromide (1-MA-3MI-Br) as functional monomer, which has π-π hydrophobic, hydrogen-bonding and electrostatic interactions with template molecule. 1-MA-3MI-Br molecularly imprinted polymers (1-MA-3MI-Br-MIPs) were used as selective sorbents for the solid-phase extraction (SPE) of water-soluble acid dyes from wastewater and soft drink. The good linearity of the method was obtained in a range of 5.0-2000 μg/L with the correlation coefficient of > 0.999. The detection limits were in a range of 0.13-0.51 μg/L for the water-soluble acid dyes in wastewater and 0.095-0.84 μg/L for those in soft drink. The mean recoveries for the acid dyes are from 89.1% to 101.0% in spiked wastewater and 91.0-101.3% in spiked soft drink. Compared with strongly anion exchange solid phase extraction (SAX-SPE), mixture anion exchange solid phase extraction (MAX-SPE), and 1-MA-3MI-Br non-imprinted solid phase extraction (1-MA-3MI-Br-NISPE), almost all of the matrix interferences were removed by 1-MA-3MI-Br-MISPE, exhibiting higher selectivity, recovery and enrichment ability for the acid dyes and better baselines in the results of HPLC analysis.     

Microstructure and structural transition in palm-kernel oil microemulsion using 1.5-order differential electroanalysis

The microemulsification in palm-kernel oil/cetyltrimethylammonium bromide/iso-pentanol/water system is investigated. The effect of iso-pentanol concentration in microemulsions on the size of single-phase microemulsion region is also discussed. It is found that the maximum microemulsion domain is obtained when iso-pentanol-to-cetyltrimethylammonium bromide mass ratio is 1.75. The diffusion coefficients of electroactive probe (ferrocene) in microemulsion microenvironment are measured by 1.5-order differential electroanalysis. The microstructure and structural transition from water-in-oil to oil-in-water microemulsions through a bicontinuous structure is examined. The results are found to be in agreement with that of conductivity measurements.     

2-甲基-3-芳基烯丙基三苯基溴代鏻的合成

取代苯甲醛经醇醛缩合、硼氢化还原、溴代反应和成盐反应合成了２-甲基-３-间硝基苯基烯丙基三苯基溴化特和２-甲基-３-对硝基苯基烯丙基三苯基溴化鏻两个化合物,收率分别达８６．４％和６９．０％。结构经ＩＲ,1ＨＮＭＰ确证。     

羧甲基纤维素系列高分子表面活性剂形成微乳液的研究

采用紫外光谱、相图、动态激光光散射、同位素示踪、光学显微镜、电导率等研究了羧甲基纤维素系列高分子表面活性剂与甲苯-水-异丙醇体系微乳液的形成过程,发现微乳液粒子大小均一,形态一致,其尺寸比低分子表面活性剂所形成的微乳液粒子大得多.醇分子插入到油水界面,改变了两相界面结构,促使微乳液的生成.电导率测定表明所形成的微乳液区均为水包油结构,即使在富含甲苯区域,亦不会有油包水的反相胶束形成.     

Conductivity of water-in-oil microemulsions stabilized by mixed surfactants

The electrical conductivity of D2O-in-n-heptane microemulsions stabilized by cationic/nonionic surfactant mixtures was studied as a function of D2O content, surfactant concentration, and surfactant mixture composition. The surfactants employed were cationic di-n-didodecyldimethylammonium bromide, DDAB, nonionic poly(oxyethylene) monododecyl ethers, C12EJ, with J=3-8 and 23, nonionic polymeric surfactants of the type PEO-PPO-PEO (Pluronic), and the reverse structure analogues (Pluronic R). Qualitative structural information was drawn from a comparison between the measured conductivity and that predicted by the charge fluctuation model for spherical droplets. The conductivity versus water content curves were found to be typical for water-in-oil systems composed of spherical droplets. From the effect of blending nonionic surfactant with DDAB on the measured conductivities, it was concluded that microemulsion conductivity is independent of the concentration of cationic surfactant (DDAB). This finding agrees well with theoretical microemulsion conductivity models.     

Cetylpyridinium bromide-based oil-in-water microemulsions as a medium for hydrolysis of esters of phosphorus acids in the presence of primary amines

High-resolution ¹H NMR technique with Fourier-transform and pulsed-gradient spin-echo was used to study the structure of oil-in-water microemulsions based on cetylpyridinium bromide. The sizes of microdrops and the distribution of components between the disperse and continuous phases were found. It was shown for the hydrolytic decomposition of O,O-bis-(p-nitrophenyl) methyl phosphonate in the presence of amines that the microemulsion medium can affect both the rate and mechanism of hydrolysis. The reaction rate constants depend on the structure of microdrops.     

Intelligent Hydrogels Via Gamma-Ray Induced Polymerization of Micellar Monomer Solutions and Microemulsions

Summary: Intelligent hydrogels were prepared upon polymerization of micellar aqueous comonomer solutions and microemulsions containing the cationic surfactant monomer 11-acryloyloxyundecyltrimethylammonium bromide (AUTMAB) and N-isopropylacrylamide (NIPAM). A chemically and physically cross-linked network structure is formed consisting of blocks of P-NIPAM and P-AUTMAB. The P-AUTMAB blocks act as physical cross-linking units improving the mechanical stability of the gel. While pure P-NIPAM hydrogels are disrupted under low compression, gels polymerized from micellar solution or microemulsion can be reversibly compressed. The presence of AUTMAB in the gel increases the swelling up to a factor of 30 compared with the pure P-NIPAM gel. Rapid and reversible swelling is observed for hydrogels with an AUTMAB content up to 2.5 wt.-%.     

β-三氯锗基丙酸及β-三苯锗基丙酸与苯基溴化镁的反应

三氯锗基丙酸(1a)和三苯锗基丙酸(2a)与过量苯基溴化镁起反应时,这两个分子中的羧基表现出一些奇特性质。当1a和2a与不同浓度的苯基溴化镁起反应时,都能生成相应的酮(3a)和醇(4a)。在稀盐酸作用下,4a极易脱水生成1,1-二苯基-3-三苯锗基丙烯-1(5a)。当1a与苯基溴化镁起反应,然后再用稀盐酸处理也同样得到5a。5a的Ge-C键能被LiAlH~4高选择性地切断,生成三苯基锗烷(6a)和1,1-二苯基丙烯(6b)。     

O-炔丙基-N,N-二(2-氯乙基)-4-氨基苯酚的合成

以对氨基苯酚（1）为原料,经氨基的羟乙基化、酚羟基的苄基保护、氯代、脱保护制得N,N-二 (2-氯乙基) -对氨基苯酚（5）;在碳酸铯作用下,5与溴丙炔经O-烷基化反应合成了新化合物--O-炔丙基-N, N-二(2-氯乙基)-4-氨基苯酚,其结构经¹H NMR, ¹³C NMR和MS表征。     

微乳液增敏作用机理探讨：显色剂在微乳液中的分配系数

与胶束体系比较，显色剂ＰＮＡ和ＣＡＳ在油／水（Ｏ／Ｗ）微乳液中具有更大的分配系数，这表明Ｏ／Ｗ微乳液比胶束体系具有更好的增敏作用是因为Ｏ／Ｗ微乳液对显色剂ＰＡＮ和ＣＡＳ具有更好的增溶与富集作用所致。     

Effect of different surfactants on colloidal and polymer properties of fluorinated acrylate latex

Fluorinated acrylate latex was successfully prepared by semi-continuous seeded emulsion polymerization of dodecafluoroheptyl methacrylate (DFMA) with butyl acrylate (BA), methyl methacrylate (MMA) initiated by potassium persulfate in the water. The resultant latexes and their films are characterized with Fourier transform infrared (FTIR) spectrometry, contact angle determinator, dynamic light scattering detector and surface tension determinator. Effect of different surfactants on colloidal and polymer properties of fluorinated acrylate latex was studied. Results show that the latex prepared with sodium dodecyl benzene sulfonate surfactant has the smallest particle size and contact angle but the moderate surface tension. The latex prepared with perfluorooctanesulfonic acid potassium surfactant has the smallest surface tension, moderate particle size but the biggest contact angle. The latex prepared with sodium 2-hydroxy-3-(methacryloyloxy) prop- ane-1-sulfonate surfactant has the biggest particle size and surface tension but moderate contact angle. In addition, the latex prepared with sodium 2-hydroxy-3-(methacryloyloxy) prop- ane-1-sulfonate has higher electrolyte stability.     

Polymerisation of liquid crystalline phases in binary surfactant/water systems

The binary phase behaviour of two potentially polymerisable quaternary ammonium surfactants in water has been investigated. Allyldodecyldimethylammonium bromide (ADAB) a single-chain surfactant displays a conventional phase progression upon increasing concentration. Whereas the doublechain analogue allyldidodecylmethylammonium bromide (ADDAB) forms two lamellar liquid crystalline phases built from surfactant bilayers, which transform via a first order phase transition. The formation of two distinct lamellar phases and their coexistence has been evidenced by optical microscopy, small-angle x-ray scattering and D₂O deuterium quadrupolar nuclear magnetic resonance spectroscopy. The lamellar phase formed at higher surfactant compositions is a normal lamellar phase (typeL ) consisting of bilayers which are on average parallel and flat. The lower compositional lamellar phase (typeL ) in contrast may not be comprised of planar bilayers but rather aggregates having a high degree of curvature in comparison to those of theL phase. The presence of the allyl polymerisable moiety in the head group position of these surfactants has the effect of reducing the rigidity of the surfactant and increasing its solubility in comparison to nonpolymerisable analogues. Polymerisation of the surfactants was attempted by using thermal and photochemical initiation in isotropic and self-assembled systems. Polymerisation occurred to approximately 30% for DADB but did not occur for ADDAB. Where polymerisation did occur the polymer was incorporated into the monomer matrix by interweaving between the surfactant aggregates. The polymers had a molecular wieght not greater than 8000 Daltons, independent of the monomer concentration of the original solution and type of polymerisation.     

Polyelectrolyte complexes of soluble poly-2-[(methacryloyloxy)ethyl]trimethylammonium chloride and its hydrogels with poly(acrylic acid)

The complex formation of poly-2-[(methacryloyloxy)-ethyl]trimethylammonium chloride (PMADQUAT) with poly(acrylic acid) (PAA) of different molecular weights has been studied in aqueous solutions by potentiometric, viscometric, turbidimetric and FTIR spectroscopic methods. The formation of insoluble non-stoichiometric polyelectrolyte complexes has been shown. The stability of polyelectrolyte complexes in solutions of different pH and ionic strength has been evaluated. The formation of polyelectrolyte complexes between hydrogels of PMADQUAT and linear PAA of different molecular weights has been studied. It was shown that the molecular weight of PAA considerably affects the kinetics of interaction as well as the final state of gel-polymer complex.     

Synthesis and some transformations of γ-(p-fluorophenyl)-γ-(2-furyl)propylamine

Ethyl α-cyano-β-(p-fluorophenyl)-β-(2-furyl)propionate was obtained by the condensation of ethyl α-cyano-β-(2-furyl)acrylate with p-fluorophenylmagnesium bromide. Its deethoxycarbonylation led to β-(p-fluorophenyl)-β-(2-furyl)propionitrile. Reduction of the nitrile with lithium aluminum hydride gave γ-(p-fluorophenyl)-γ-(2-furyl)propylamine. Some transformations of the latter were studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 503–509, April, 2006.     

Functionalized latexes as substrates for atom transfer radical polymerization

The application of atom transfer radical polymerization (ATRP) to the homopolymerization of 2‐hydroxyethyl acrylate and 2‐(methacryloyloxy) ethyl trimethylammonium chloride at the surface of a crosslinked polystyrene latex functionalized with alkyl bromide groups is reported. Polymerization was carried out using the surface groups of the dialyzed latex as initiators. The resulting hydrophobic core, hydrophilic shell latexes, were analyzed by FTIR, ¹³C‐NMR spectroscopy, and dynamic light scattering.